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[ CAS No. 1592-38-7 ] {[proInfo.proName]}

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3d Animation Molecule Structure of 1592-38-7
Chemical Structure| 1592-38-7
Chemical Structure| 1592-38-7
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Product Details of [ 1592-38-7 ]

CAS No. :1592-38-7 MDL No. :MFCD00004124
Formula : C11H10O Boiling Point : -
Linear Structure Formula :- InChI Key :MFGWMAAZYZSWMY-UHFFFAOYSA-N
M.W : 158.20 Pubchem ID :74128
Synonyms :

Calculated chemistry of [ 1592-38-7 ]

Physicochemical Properties

Num. heavy atoms : 12
Num. arom. heavy atoms : 10
Fraction Csp3 : 0.09
Num. rotatable bonds : 1
Num. H-bond acceptors : 1.0
Num. H-bond donors : 1.0
Molar Refractivity : 50.08
TPSA : 20.23 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.7 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.08
Log Po/w (XLOGP3) : 2.21
Log Po/w (WLOGP) : 2.18
Log Po/w (MLOGP) : 2.56
Log Po/w (SILICOS-IT) : 2.85
Consensus Log Po/w : 2.38

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 2.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -2.76
Solubility : 0.273 mg/ml ; 0.00172 mol/l
Class : Soluble
Log S (Ali) : -2.27
Solubility : 0.851 mg/ml ; 0.00538 mol/l
Class : Soluble
Log S (SILICOS-IT) : -3.89
Solubility : 0.0204 mg/ml ; 0.000129 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.0

Safety of [ 1592-38-7 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 1592-38-7 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 1592-38-7 ]

[ 1592-38-7 ] Synthesis Path-Downstream   1~92

  • 1
  • [ 1592-38-7 ]
  • [ 66-99-9 ]
YieldReaction ConditionsOperation in experiment
100% With dimethyl selenoxide In benzene for 5h; Heating;
100% With Nitrous oxide In 1,2-dichloro-ethane at 120℃; for 9h;
100% With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In <i>tert</i>-butyl alcohol for 1h; Reflux;
100% With oxygen In 1,3,5-trimethyl-benzene at 60℃; for 9h; 8.8 Example 8 Application of this method in the reaction of other alcohols to aldehydes and ketones The typical reaction steps are as follows:1 mmol of the starting alcohol of the reactant column shown in Table 2,OH - Ni3In-LDH 14 mg,Mesitylene 5mL were added to the reactor,Into the oxygen,Atmospheric reaction,The reaction was stirred at 60 for a certain period of time.The solid catalyst was removed by filtration,Using gas chromatography internal standard method (chlorobenzene as internal standard) to analyze the content of liquid products,Calculate yield.
100% With 1-methyl-1H-imidazole; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen In acetonitrile at 60℃; for 20h;
99% With polymeric complex of oxodiperoxochromium(VI) compound and pyrazine (Pyz-CrO5)n In dichloromethane for 0.6h; Ambient temperature;
99.9% With silica-supported Jones reagent In dichloromethane for 0.00269444h;
99% With sulfur(VI) fluoride; potassium carbonate; dimethyl sulfoxide at 20℃; for 12h; chemoselective reaction;
98% With 4-dimethylaminopyridine; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper trifluoromethanesulfonate; (S)-(-)-5-(2-pyrrolidinyl)-1H-tetrazole at 25℃; for 1h; chemoselective reaction; 4 4.1.2. The oxidation of primary alcohols General procedure: A round-bottom flask was charged with alcohol (2 mmol), CuOTf (0.1 mmol, 0.05 equiv) (S)-5-(pyrrolidin-2-yl)-1H-tetrazole (0.1 mmol, 0.05 equiv), TEMPO (0.1 mmol, 0.05 equiv), DMAP (0.15 mmol, 0.075 equiv) and CH3CN (5 ml). The reaction mixture was stirred at 25 °C open to air until the completion of the reaction, as monitored by TLC. After completion, CH3CN was evaporated under vacuum. The residue was then diluted with CH2Cl2 (5 ml) and filtered through a plug of silica gel to afford the desired product.
96% With Merrifield's resin-bound N-aminoimidazolium chlorochromate In dichloromethane for 24h; Heating;
96% With potassium carbonate; chlorobenzene; 2-dicyclohexylphosphino-1,1'-biphenyl In toluene at 105℃; for 6h;
96% With (2-((2,6-diisopropylphenyl)amino)-4-((2,6-diisopropylphenyl)imino)-pent-2-ene) lithium salt; oxygen; gold(I) chloride In toluene at 90℃; for 10h;
96% With aluminium(III) chloride; 1-decyl-4-aza-1-azoniabicyclo[2.2.2]octane chlorochromate In acetonitrile for 1.5h; Heating;
96% With iron nitrate (III) at 60℃; for 0.5h;
96% With potassium carbonate; chlorobenzene In toluene at 105℃; for 6h;
96% With potassium peroxomonosulfate; 3,3'-diiodo-2,2',6,6'-tetramethoxy-4,4'-biphenyldicarboxylic acid In nitromethane at 30 - 35℃; for 16h;
96% With oxygen; HNO3; 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane; lithium hydroxide monohydrate at 20℃; for 18h; Sealed tube;
96% With sodium chlorine monoxide; Sodium hydrogenocarbonate; potassium bromide In dichloromethane at 0℃; for 0.25h;
95% With IBS; potassium peroxomonosulfate; N-hexadecyl-N,N,N-trimethylammonium bromide In lithium hydroxide monohydrate at 20℃; for 2h; Green chemistry; chemoselective reaction; IBS-catalysed alcohol oxidation in CTAB micelle; general procedure General procedure: The alcohol (2 mmol) was added to a solution of IBS (0.02 mmol, 0.01 eq), oxone (2.2 mmol, 1.1 equiv.) and 3 wt% CTAB solution (5 mL). The mixture was stirred at room temperature. The reaction was monitored by TLC. After completion, the solution was extracted with CH2Cl2 (3 × 10 mL). The combined organic phase was then filtered through a pad of silica gel and evaporated under vacuum to afford the desired product.
95% With sodium chlorine monoxide; C186H204N12O36; Sodium hydrogenocarbonate; potassium bromide In dichloromethane; lithium hydroxide monohydrate at 0 - 15℃; for 1.5h;
95% With (diacetoxyiodo)benzene In dichloromethane at 20℃; for 5h;
95% With sodium chlorine monoxide; Sodium hydrogenocarbonate; potassium bromide In dichloromethane; lithium hydroxide monohydrate at 0℃; for 0.166667h; Schlenk technique;
94% With 3-(tert-butoxycarbonyl amino)-9-azabicyclo[3.3.1]nonane N-oxyl; oxygen; NaNO2 In glacial acetic acid at 25℃; for 0.9h; Typical procedure for the aerobic oxidation of p-methylbenzyl alcohol to p-methyl benzaldehyde (Table 2, entry 2): General procedure: A 25-mL tube equipped with a magnetic stirrer bar was added p-methylbenzyl alcohol (0.122 g, 1 mmol), sodium nitrite (5.5 mg, 8 mol%) and 3-(tert-butoxycarbonyl amino)-9-azabicyclo[3.3.1]nonane N-oxyl (3-BocNH-ABNO) (7.7 mg, 3 mol%). After the air in the tube was replaced with O2, 1 mL of acetic acid was added with syringe. Then the mixture was stirred under dioxygen atmosphere (balloon) at room temperature until the reaction was completed. After the reaction was finished, to the reaction mixture was added 8 mL of diethyl ether. Then the mixture was transferred into a separation funnel, and washed with saturated sodium bicarbonate solution (10 mL×3). The aqueous phase was extracted with 8 mL of ether. The combined organic phases was concentrated on a rotary evaporator and the residue was purified by column chromatography on silica gel using petroleumether/diethyl ether as eluent to afford p-methyl benzaldehyde as a colorless liquid; yield: 0.108 g (90%).
94% With di-tert-butyl-diazodicarboxylate; bathophenanthroline; oxygen; Cs2CO3; copper chloride (I) In toluene at 20℃; for 3h;
94% With double-atom catalyst FeCo-DAC In o-dimethylbenzene at 140℃; for 36h; Inert atmosphere; Sealed tube;
93% With piridinium dichromate; adogen 464; dihydrogen peroxide; anhydrous sodium carbonate In various solvent(s) for 24h; Heating;
93% Stage #1: 2-Naphthalenemethanol With (-N(SO2C8F17)-(biphenyl-2,2'-diyl)-O-)AlCH3 In toluene at 21℃; for 0.5h; Stage #2: With 2,2-dimethypropanal In toluene at 21℃; for 1h; Further stages.;
93% With oxygen; potassium carbonate In toluene at 90℃; for 10h;
92% With aluminium(III) chloride; 1-butyl-4-aza-1-azoniabicyclo[2.2.2]octane chlorochromate In acetonitrile for 2h; Heating;
92% With HNO3; diphosphorus pentoxide; mesoporous silica for 0.0666667h;
92% With triphenylmethylphosphonium dichromate at 20℃; for 0.0666667h; Neat (no solvent); chemoselective reaction;
92% With ammonium nitrate; hydrogenchloride; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen In lithium hydroxide monohydrate; acetonitrile at 60℃; for 5h; Green chemistry;
92% With ammonium nitrate; hydrogenchloride; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In acetonitrile at 60℃; Green chemistry; chemoselective reaction;
92% With dihydrogen peroxide In neat (no solvent) at 50℃; for 0.166667h; General experimental procedure for the oxidationreaction General procedure: Substrate (5 mmol) and ZPFe (0.5 mol %) were added intoa 25 cm3 two-necked flask. It was heated in an oil bath to50 °C and then, 30 % H2O2 (0.015 mol) was added slowlywith continuous stirring for the specified time. The reactionprogress was monitored by GC. At the end, the reactionmixture was cooled to room temperature and then, thecatalyst was removed from the reaction mixture by centrifuge.After that, the organic layer was separated from theaqueous phase by extraction with n-hexane and dried overanhydrous CaCl2. The identity of reaction products wasconfirmed by FT-IR, GC-MS, and 1H NMR.
92% With 5H3N*5H(1+)*IMo6O24(5-); oxygen; sodium chloride In lithium hydroxide monohydrate; acetonitrile at 70℃; for 24h; Green chemistry;
92% With C20H26B10Cl2N8NiO4 In toluene at 20℃; for 4h; 9 Dissolve 2-naphthalenemethanol (1.0mmol) and nickel complex 3 (0.02mmol) in 2mL of toluene, and let the air react for 4 hours at room temperature. After completion, the concentrated reaction solution was directly separated by silica gel column chromatography (petroleum ether: two Chloromethane=3:1), dry to the same quality, obtain the corresponding product C11H8O (yield 92%), the reaction formula is:
91% With orthoperiodic acid In acetonitrile at 20℃; for 18h;
91% With dihydrogen peroxide at 60℃; for 0.333333h; Green chemistry;
90% With Pyridine-2,6-dicarboxylic acid; dihydrogen peroxide; trifluoroacetic acid; anhydrous zinc bromide In tetrahydrofuran; lithium hydroxide monohydrate at 20℃; for 16h;
90% With C30H56AgN4(1+)*C2F3O2(1-); potassium-t-butoxide In toluene at 20℃; for 4h; Darkness;
90% With C38H32N2O12Ru3; N-Methylmorpholine N-oxide In acetonitrile for 0.0833333h; Reflux; Inert atmosphere; Schlenk technique;
89% With manganese(IV) oxide; oxygen In toluene at 110℃; for 8h; Green chemistry; 3.1. Oxidation of benzhydrol 1a in the presence of substoichiometric amounts of activated MnO2: preparation of benzophenone 2 (Table 1, entry 6). General procedure General procedure: Benzhydrol 1 (0.3831 g, 2.08 mmol) was dissolved in toluene (15 mL) and activated MnO2 (purchased from Aldrich, 0.106 g, 1.92 mmol, 50 mg/mmol) was added to the solution. The reaction mixture was heated at 110 °C under oxygen atmosphere for 4 h. Supernatant of the reaction mixture was scooped by pipet. Additional toluene (5 mL) was added to solid residue and washed the solid then the supernatant was scooped by pipet. This washing procedure was repeated for four times. All of toluene solution was combined and concentrated. Crude product was purified by flash chromatography (silica gel/hexane-EtOAc 3:1) to give 2 in 98% yield (0.373 g, 2.05 mmol). MnO2 residue was examined for the recycling use of the oxidant (Scheme 4, see below).
89% With tert.-butylhydroperoxide; Eosin In decane; acetonitrile at 25℃; for 32h; Inert atmosphere; Irradiation; Molecular sieve; Green chemistry; chemoselective reaction; General procedure for oxidation of alcohols: General procedure: Oven dried round bottom flask was charged with Eosin Y (5 mmol) alcohol (1 mmol) and 3 equiv. of TBHP (5.5 M in decane) in dry ACN. The resulting mixture was degassed for 15 mins, followed by back filling N2, and then irradiated under Blue LED light (12W, 455 nm) at room temperature (25 oC). After reaction completion monitored through TLC, the mixture was diluted with 15 ml of 10% NaHCO3 solution, and extracted with EtOAc (3 × 20 ml). The combined organic extracts were washed with brine (20 ml), dried over Na2SO4, and concentrated on vacuo. Purification of the crude product on silica gel using EtOAc:Hexane as solvent system afforded the desired product.
88% With (NH4)4[CuMo6O18(OH)6]·5H2O; oxygen; sodium chloride In lithium hydroxide monohydrate; acetonitrile at 60℃; for 20h;
88% With sodium chlorine monoxide; C8H16NO3; tetrabutylammonium bromide; Sodium hydrogenocarbonate; potassium bromide In dichloromethane; lithium hydroxide monohydrate at 0℃; for 0.5h; chemoselective reaction; General procedure for the oxidation using NaOCl General procedure: A 50ml flask was charged with a solution of benzyl alcohol, morpholinone nitroxide 2 in CH2Cl2 and a sat. aqueous solution of NaHCO3 containing KBr and n-Bu4NBr. To this cooled to 0 °C by water-ice bath and well stirred mixture, a pre-mixed solution of aqueous NaOCl (6-14% Cl) and sat. aqueous solution of NaHCO3 was added dropwiseduring 10 min. The reaction was stirred for 30 min at 0 °C, then quenched with sat. aqueous solution of Na2S2O3. The aqueous layer was separated and extracted with CH2Cl2. The combined organic layers were washed with brine, dried over Na2SO4 and concentrated under reduced pressure. The crude material was purified by flash column chromatography to give benzaldehyde as a colorless oil.
87% With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [Cu2(1,2-benzenedicarboxylate)2(1,4-bis(1,2,4-triazol-1-ylmethyl)-2,3,5,6-tetrafluorobenzene)2]·3H2O}n; anhydrous sodium carbonate In acetonitrile at 75℃; for 16h; 2.2 Catalytic reaction General procedure: In a typical experiment, 4-methoxybenzyl alcohol (12μL, 0.1mmol), Cu-FMOF (11.3mg, 10mmol %), TEMPO (7.8mg, 0.05mmol) and NaCO3 (10.6mg, 0.1mmol) in 1mL of air saturated acetonitrile were taken in a 15-mL three-necked round-bottom flask. The solution was magnetically stirred for 16h at 75°C under air atmosphere. The progress of the reaction was monitored via gas chromatography (Shimadzu GC-2010AF) involving a Chromopak capillary column and flame ionization detector. The products were further confirmed by using gas chromatography-mass spectroscopy (GC-MS) (Shimadzu GCMS-2010). The concentrations of 4-methoxybenzyl alcohol and 4-methoxybenzylaldehyde were calibrated by external standard method with standard samples (see Fig. S1).
86% With pyridinium chlorochromate supported on montmorillonite KSF for 0.25h; Milling; Typical procedure for the oxidation and oxidative deprotection reactions General procedure: A mixture containing the PCC supported on KSF (1.7 g) and the substrate (0.5 mmol)was introduced into a clean and dry ball-milling vessel (grinding jar 12 mL) with twostainless steel grinding balls (d 15 mm). Next, the milling process was started at350 rpm for the time mentioned in Tables 2 and 3 and the progress of the reaction wasscreened by TLC (n-hexane, ethyl acetate 9:1). After completion, the resulting solid mixturewas washed with diethyl ether (2310 mL) and then the obtained filtrate was concentratedunder reduced pressure. Eventually, further purification was carried out bycolumn chromatography on silica gel (n-hexane/ethyl acetate, 9:1) if it was required. Allof the products were known compounds, identified on the basis of matching meltingpoints (for solids), Rf values (for liquids) and 1H-NMR and 13CNMR spectra with thosein the literature cited in Tables 2 and 3. Original spectra were submitted for review andare available in the Supplementary Materials or from the corresponding author uponrequest. For the sake of completeness, representative data are provided below.
84% With iodine; oxygen In ethyl acetate at 20℃; for 24h; visible light irradiation;
84% With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione at 60℃; for 3h;
84% With Pd(0) nanoparticle supported on aminopropyl grafted silica-based mesocellular foam; air In para-xylene at 110℃; for 5h;
83% With potassium osmate(VI) dihydrate; chloramine-T In lithium hydroxide monohydrate; <i>tert</i>-butyl alcohol for 1h; chemoselective reaction; oxidation of allylic and benzylic alcohol General procedure: Chloramine-T (0.5 equiv) was added to a solution of K2[OsO2 (OH)4] (3 mol%) in t-BuOH/H2O (1:1) followed by the addition of alcohol (1.0 mmol) and kept on stirring till completion (confirmed by TLC). The reaction was quenched by adding sodium sulphite(Na2SO3) and stirred for 30 min. The mixture after extraction with ethyl acetate (twice), usualworkup and purification over silica gel column using Hexane:EtOAc (95:5) afforded pure products.
83% With oxygen In neat (no solvent) at 100℃; for 6h; Condition B General procedure: A mixture of the substrate (250 μmol) and10% Ru/C (12.6 mg, 12.5 μmol) was stirred at 100 °C using atest tube equipped with air balloon. After the correspondingreaction time, the mixture was filtered through a membranefilter (pore size: 0.2 μm). The catalyst on the filter was washedwith H2O and CH2Cl2 and extracted with CH2Cl2 (5 mL × 3).The combined organic layers were dried over Na2SO4 andconcentrated in vacuo. The residue was further purified bysilica-gel column chromatography
83.5% With oxygen; C54H60N6O6Pd(2+)*2Br(1-); potassium carbonate In toluene at 80℃; for 8h; Autoclave;
82% With sodium wolframate; dihydrogen peroxide; methyl tri-n-octyl ammonium hydrogen sulfate In lithium hydroxide monohydrate at 90℃; for 4.5h;
82% With dihydrogen peroxide; methyl tri-n-octyl ammonium hydrogen sulfate In lithium hydroxide monohydrate at 90℃; for 4.5h;
82.5% With dihydrogen peroxide In tetrahydrofuran; lithium hydroxide monohydrate at 50℃; for 10h; 14 Embodiment 14 The 1.05 g (0.0066 µM) of 2 - naphthalene methanol GO - Ti compound 0.4 g dispersed in 10 ml in tetrahydrofuran and in the oil bath heated to 50 °C, 1.5 g (0.0132 µM) of 30 wt % aqueous hydrogen peroxide solution in tetrahydrofuran is slowly added. After adding after keeping the temperature reaction 10 h, by HPLC detection 2 - naphthalene methanol conversion rate of 87.6%, 2 - naphthalene formaldehyde selectivity of 98.8%. The concentrated filtrate after filtering to remove the catalyst, after separation by silica gel column chromatography to obtain 2 - naphthalene formaldehyde 0.85 g, yield 82.5%.
82% With (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; tetra-n-butylammonium azide In acetonitrile at 25℃; for 12h; Irradiation;
81% Stage #1: 2-Naphthalenemethanol With oxalyl dichloride; dimethyl sulfoxide In dichloromethane at -78℃; for 0.25h; Stage #2: With triethylamine In dichloromethane at 20℃;
81% With aluminum(III) oxide; [Ru(2,2′-bipyridine)2(2,2′-bipyridine-5,5′-dicarboxylic acid)Cl2]; oxygen In acetonitrile for 12h; Irradiation;
79% With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In aq. buffer at 40℃; for 10h;
78% With C16H13ClIrNO(1-); sodium methoxide In toluene for 20h; Reflux; Inert atmosphere;
78% With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; dimethyl 3-methyl-9-oxo-7-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)-2,4-di(pyridin-2-yl)-3,7-diazabicyclo-[3.3.1]nonane-1,5-dicarboxylate; copper(II) bromide In lithium hydroxide monohydrate at 20℃; for 12h; Green chemistry;
77% With hydrogen bromide; oxygen; NaNO2 In lithium hydroxide monohydrate; acetonitrile at 80℃; for 48h;
76% With chromium(VI) oxide; orthoperiodic acid In dichloromethane; acetonitrile at -78℃; for 1h;
75% With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In n-heptane at 80℃; for 24h; Synthesis of Aldehydes 2a-y; General Procedure General procedure: A mixture of catalyst PS-PEG-TD2-Cu(OAc)2 (100 mg, 0.05mmol Cu), BnOH (1a, 27.0 mg, 0.25 mmol), and TEMPO (7.8 mg,0.05 mmol) in heptane (2.0 mL) was stirred at 80 °C for 24 hunder air (1 atm). The mixture was then cooled and filtered, andthe resulting solid material was washed with Et2O (3 × 2 mL).The organic phases were combined, concentrated to a volume of2 mL, and the internal standard was added to determine the GCyield. The crude product was purified by column chromatography[silica gel, hexane-Et2O (99:1)]. In the formation of somebenzaldehydes, low isolated yields were observed because ofinstability of the benzaldehydes on silica gel
70% With iodine; oxygen In acetonitrile at 20℃; for 6h; Irradiation;
67% With 5-chloro-2,3-dihydro-1H-inden-1-one; potassium carbonate In nitrobenzene at 160℃; for 15h; Inert atmosphere; Green chemistry;
61% With tripotassium phosphate tribasic; carbon dioxide In dimethyl sulfoxide at 90℃; for 48h;
61% With cerium(III) trichloride heptahydrate; Sodium hydrogenocarbonate In acetonitrile at 50℃; for 42h; Irradiation; Sealed tube; General procedure (GP1) General procedure: A 10 mL glass vial equipped with a teflon-coated stirring bar was charged with benzylic alcohol 1 (0.2 mmol), CeCl3·7H2O (10 mol %), and NaHCO3 (10 mol%). The glass vial was sealed with a PTFE septum. Then, solvent (2 mL) was added and the reaction was opened to air via a needle. The reaction was placed in a pre-programed temperature (50 °C) controlled blue LED reactor (as shown in Figure S1) and the reaction mixture was irradiated with a 455 nm blue LED. After 35-48 hours, the reaction mixture was concentrated under reduced pressure. Product 2 was purified by flash chromatography on silica using hexane and AcOEt.
58% With acetic anhydride; glacial acetic acid In dimethyl sulfoxide at 70℃; for 0.166667h; Microwave irradiation; Green chemistry; 6 Example 6 6a (0.63mmol, 0.1g), DMSO 1.95mL, Ac2O 1.36mL, AcOH 0.24mL were sequentially added to a 15mL microwave reaction tube, microwave power 150w, heating temperature 70°C, reaction time 10min,After cooling, NaHCO3 solution was added and stirred at room temperature for 30 min. Extract with ethyl acetate, collect the organic phase, and extract the aqueous phase with ethyl acetate 2-3 times.The organic phases were combined, washed with water in sequence, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 6b (yield: 58%).
57% With ammonia hydrochloride In 1,3,5-trimethyl-benzene at 140℃; for 3h;
56% With Nitrogen dioxide In acetonitrile at 140℃; for 5h; Sealed tube; 2.2. General procedure for the aerobic oxidation of various substrates General procedure: To a dried 45 mL tube equipped with a magnetic stirring, 2 mL acetonitrile, 0.5 mmol substrate and 0.046 mmol NO2 were sequentially added (note: the air in the tube was not removed). Then the reaction tube was sealed and stirred magnetically at a constant-temperature to perform the reaction for 5 h. Once the reaction time was reached, GCanalysis of the mixture provided the GC yields of the products. Then the crude product from another parallel experiment was purified by silicagel chromatography to give the desired product.
51% With indium(III) isopropoxide; 2,2-dimethypropanal In chloroform at 20℃; for 3h; Glovebox; Sealed tube; Inert atmosphere; Oppenauer Oxidation of Alcohols Using In(i-OPr)3; General Procedure General procedure: To a screw tube in a glovebox was added In(Oi-Pr)3 (29.2 mg, 0.1 mmol). The tube was then sealed and removed from the glovebox, and CHCl3 (1 mL), alcohol (0.5 mmol), and pivalaldehyde (280 μL, 2.5 mmol) were added under N2 in this order. After stirring the mixture at r.t. for 3 h, H2O (1.0 mL) was added to the reaction mixture, which was then extracted with EtOAc. The organic phase was dried (Na2SO4), and evaporated under reduced pressure. The crude material was purified by silica gel column chromatography (Table 2 and Scheme 2).
50% With tetrakis(pyridine)silver(II) peroxodisulfate In acetonitrile for 3h; Heating;
With N-chloro-succinimide
With chromic acid
94 % Turnov. With piridinium dichromate; dihydrogen peroxide; anhydrous sodium carbonate In 1,2-dichloro-ethane at 80℃; for 24h;
With K10-montmorillonite clay-supported tetrabutylammonium periodate In 2,2,4-trimethypentane for 4h; Heating; Yield given;
With Nitrous oxide In 1,2-dichloro-ethane at 120℃; for 9h;
With potassium carbonate; chlorobenzene; 2-dicyclohexylphosphino-1,1'-biphenyl In toluene at 105℃; for 6h;
Stage #1: 2-Naphthalenemethanol With diphosphorus pentoxide at 20℃; for 0.00833333h; Stage #2: With HNO3 at 20℃; for 0.0666667h;
With Dess-Martin periodane In dichloromethane at 20℃; for 1h; Inert atmosphere; Representative experimental procedure: Galactopyranose derivative 24: To 1,2:3,4-di-O-isopropylidene-d-galactopyranose (23) (64 mg, 0.25 mmol) in dry CH2Cl2 (5 mL) at rt under argon was added DMP (209 mg, 0.49 mmol) and the mixture stirred for 1 h. Montmorillonite K10 (50 mg) was then added followed by potassium allyl trifluoroborate (73 mg, 0.49 mmol) and the mixture stirred for 1 h before adding a further portion of DMP (261 mg, 0.62 mmol). After stirring for a further 1 h, the reaction was quenched with sat. aq NaHCO3 (5 mL) and sat. aq Na2S2O3 (5 mL) and allowed to stir for 1 h before diluting with brine (10 mL) and CH2Cl2 (10 mL). The mixture was filtered and then the layers separated. The aqueous portion was further extracted with CH2Cl2 (2 × 5 mL) and the combined organic extracts dried (Na2SO4) and concentrated in vacuo. The residue was purified by silica gel chromatography (0-5% acetone in CH2Cl2) to give the compound 24 (55 mg, 75%) as a colourless micro-crystalline solid, mp 47-49 °C; Rf (CH2Cl2) = 0.15; vmax/cm-1 (thin film) 2988, 2936, 1723 (CO), 1383; [α]D -144 (c 0.4, CH2Cl2); δH (400 MHz, CDCl3) 5.97 (1H, ddt, J = 17.0, 10.5, 7.0, H-8), 5.64 (1H, d, J = 5.0, H-1), 5.20-5.08 (2H, m, H-9), 4.63 (1H, dd, J = 8.0, 2.5, H-3), 4.56 (1H, dd, J = 8.0, 2.0, H-4), 4.35 (1H, dd, J = 5.0, 2.5, H-2), 4.22 (1H, d, J = 2.0, H-5), 3.50 (1H, ddt, J = 18.5, 7.0, 1.5, H-7a), 3.33 (1H, ddt, J = 18.5, 7.0, 1.5, H-7b), 1.49 (3H, s), 1.44 (3H, s), 1.33 (3H, s), 1.30 (3H, s); δC (100 MHz, CDCl3) 207.2 (C-6), 130.0 (C-8), 118.7 (C-9), 109.6, 109.0, 96.4 (C-1), 73.5 (C-5), 72.3 (C-4), 70.6 (C-3), 70.4 (C-2), 44.6 (C-7), 25.9, 25.8, 24.8, 24.2; m/z (ESI) 321 [M+Na]+; [HRMS (ESI): Calcd for C15H22NaO6, 321.1309. Found: [M+Na]+, 321.1317 (-2.7 ppm error)]; [C15H22O6 requires C, 60.39; H, 7.43. Found C, 60.35; H, 7.35].
> 99 %Chromat. With tert.-butylnitrite; oxygen In glacial acetic acid at 40℃; for 3.5h; chemoselective reaction;
With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In dimethyl sulfoxide at 20℃; General procedure for the one-pot conversion of alcohols to benzimidazoles: In a typical experiment, the primary alcohol (0.5-0.6 mmol) and IBX (1.1 equiv) were stirred in DMSO at ca. 20 °C. Once the oxidation of alcohol to aldehyde was complete, as judged from TLC analysis, o-phenylenediamine (1.1 equiv) was introduced into the reaction mixture and the reaction mixture was allowed to stir at room temperature until the aldehyde disappeared. At the end of the reaction, DMSO was removed under high vacuum, and the residue was treated with 1.0 M NaHCO3 solution until the pH was 8-9. The organic matter was extracted with ethyl acetate. Regular work-up followed by silica-gel column chromatography led to pure benzimidazoles, which were characterized spectroscopically.
With 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid); Cupric sulfate; oxygen; horseradish peroxidase at 20℃; for 20h; Microbiological reaction; aq. phosphate buffer; Enzymatic reaction;
82 %Spectr. With oxygen; anhydrous sodium carbonate In lithium hydroxide monohydrate at 100℃; for 24h; Green chemistry;
90 %Chromat. With Isopropenyl acetate; C16H21ClIrNO In toluene at 80℃; for 10h; Inert atmosphere; General Procedure for the Hydrogen Transfer Oxidation of Benzylic Primary Alcohols Shown in Table 4 General procedure: Under an atmosphere of argon, catalyst 2e (2.0 mol%), benzylic primary alcohol (1.0 mmol), isopropenyl acetate (1.0 mmol), and toluene (18 mL) were placed in a flask. The mixture was stirred at 80 °C for 10 h. The conversion of benzylic primary alcohol and the yield of benzaldehyde derivative were determined by GC analysis using biphenyl as an internal standard.
With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; Trametes versicolor laccase; oxygen In acetonitrile at 20℃; for 24h; Enzymatic reaction;
With [bis(acetoxy)iodo]benzene; tetrabutylammonium bromide In ethyl acetate at 20℃; for 24h; Oxidation Procedure General procedure: Alcohol (1 mmol) was added to amixture of BAIB (1.1 mmol) and bromide anions (0.2 mmol) inEtOAc (1.5 mL), and the mixture was stirred at room temperaturefor 24 h. The solvent was removed under reduced pressureand the crude product was checked by 1H NMR spectroscopy. Incase of p-nitrobenzyl alcohol, anisole, and p-chlorobenzylalcohol oxidations, the residue was purified by chromatography[PE to separate iodobenzene and PE-EtOAc (10:1) to separatethe corresponding aldehyde].
With oxygen; potassium carbonate In lithium hydroxide monohydrate at 80℃; for 12h; Green chemistry;
With lithium hydroxide monohydrate; iodine; oxygen In isopropanol for 22h; Irradiation; [3-(4-Bromophenyl)oxiran-2-yl](phenyl)methanone (3aa);9 Typical Procedure General procedure: I2 (0.315 mmol, 1.05 equiv) and styrene (0.6 mmol, 2 equiv) wereadded to a solution of 4-bromobenzyl alcohol (0.3 mmol, 1 equiv) andH2O (100 μL) in i-Pr2O (3 mL) in a Pyrex test tube under O2. The mixturewas stirred and externally irradiated with four 22 W fluorescentlamps for 22 h. LiOH·H2O (1.8 mmol, 6 equiv) was then added, and thesolution was stirred for a further 2 h under air. The reaction wasquenched with sat. aq Na2S2O3 and the mixture was extracted withEtOAc. The organic layers were combined, dried (MgSO4), and concentratedin vacuo. The crude residue was purified by column chromatography[silica gel, hexane-EtOAc (5:1)] to give a white solid; yield:61.9 mg (0.20 mmol, 68%).
With potassium carbonate In lithium hydroxide monohydrate at 40℃; for 6h; Irradiation;
With tert.-butylhydroperoxide at 70℃; for 8h;
With C74H52F2Fe2N2O10S; dihydrogen peroxide; urea In dichloromethane at 20℃; for 0.5h;
14 %Spectr. With Rh(cod)Cl<SUB>2</SUB> at 177℃; for 16h; Schlenk technique; Inert atmosphere;
With iron(II) perchlorate; dihydrogen peroxide; α-cyclodextrin-6A,6D-dicarboxylic acid In lithium hydroxide monohydrate; acetonitrile
With Co(at)N-doped carbon yolk-shell nanocomposite; air In lithium hydroxide monohydrate at 110℃; for 6h; Schlenk technique;
With 1,10-Phenanthroline; dihydrogen peroxide; bromine In acetonitrile for 1.5h; Reflux; Catalytic oxidation of benzyl alcohols and hydrocarbons in the presence of silica-coated magnetic nanoparticle-supported NHPI General procedure: Oxidation of benzyl alcohols and hydrocarbons was carriedout in a 50-ml round-bottomed flask equipped witha condenser and a mechanical stirrer. Hydrogen peroxide(aqueous solution 30% (w/w) of H2O2)was used asoxidant. In a typical procedure, to a mixture acetonitrile(5.0 ml) solution of benzyl alcohol (1 mmol) wasadded catalyst (10 mg), o-phenanthroline (2.5 mol%), Br2(3 mol%) and the H2O2(2 mmol). Then, the reaction mixturewas heated at reflux temperature. After completion ofthe reaction, the catalyst was magnetically separated andthe products were analysed using GC-MS measurements.Additionally, under the same reaction conditions, reactivityof tetralin and indane was examined and excellentconversion with high selectivity was observed.
With sodium hypochlorite; C42H42N28O14*C9H18NO In chloroform-d1 at 25℃; for 2h;
79 %Chromat. With oxygen In acetonitrile at 70℃; for 7.8h; chemoselective reaction;

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  • 2
  • [ 1592-38-7 ]
  • [ 939-26-4 ]
YieldReaction ConditionsOperation in experiment
98% With pyridine; phosphorus tribromide In benzene at 55℃; for 6h;
95% With hydrogen bromide In acetic acid for 1h;
91% With N-Bromosuccinimide; potassium hexamethylsilazane; (1,3,4)-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene In dichloromethane at 20℃; for 6h; Inert atmosphere;
89% With tetra-(n-butyl)ammonium iodide; ethylene dibromide; triphenylphosphine at 60℃; for 2h; Sealed tube; Inert atmosphere;
87% With phosphorus tribromide at 0 - 20℃; for 20h;
82% With phosphorus tribromide In dichloromethane at 0 - 20℃; for 4h;
With pyridine; phosphorus tribromide; benzene
With pyridine; phosphorus tribromide
With hydrogen bromide In diethyl ether 1.) -30 deg C, 5 min; 2.) room temp., 3 h; Yield given;
With phosphorus tribromide In diethyl ether
With phosphorus tribromide In diethyl ether at -40℃;
With phosphorus tribromide In tetrahydrofuran at -78℃; 91 Triphenylphosphonium salts: Cinnamyl triphenylphosphonium chloride, 1-naphthylmethyl triphenylphosphonium chloride, methoxymethyltriphenylphosphonium chloride and 2-methybenzyl triphenylphosphonium bromide are available commercially, where as 3-methoxybenzyl triphenylphosphonium chloride, 3,5-dimethoxybenzyl triphenylphosphonium chloride, 2,4-dimethylbenzyl triphenylphosphonium chloride were prepared by refluxing triphenylphosphine with a slight excess of the corresponding chloride in toluene for 4 h. 4-Trifluomethylbenzyl triphenylphosphonium bromide, 3-furomethyltriphenylphosphonium bromide, 2-naphthylmethyltriphenylphosphonium bromide, 3,5-difluorobenzyl triphenylphosphonium bromide, 4-(t-butyldimethylsilyloxymethyl)benzyltriphenylphosphonium 2t bromide, 4-(N-t-Boc-aminomethyl)benzyltriphenylphosphonium bromide and 3-(N-t-Boc-amino)benzyltriphenyl-phosphonium bromide were prepared by treating the corresponding bromides with triphenylphosphine in toluene at room temperature for 12 h. 4-(Carboxymethyl)benzyltriphenylphosphoniumbromide was prepared by treating the bromide with triphenylphosphine in 5:1 toluene/THF solution at room temperature for 48 h. 3-furonmethylbromide, 2-naphthalenelmethylbromide and 3-(N-t-Boc-amino)benzylbromide were produced respectively from 3-furonmethanol, 2-naphthalenemethanol and 3-(N-t-Boc-amino)benzylalcohol upon treatment with PBr3 in THF at -78° C.ref 3-furonmethanol and 2-naphthalenemethanol are available commercially. 3-(N-t-Boc-amino)benzylalcohol was prepared from a commercial sample of 3-aminobenzylalkohol. 4-(t-butyldimethylsilyloxymethyl)benzylbromide and 4-(N-t-Boc-aminomethyl)benzylbromide were prepared from commercial samples of 4-hydroxymethylbenzoic acid methylester and 4-aminomethylbenzoic acid respectively using the following experimental procedures.
With pyridine; phosphorus tribromide In toluene at 0 - 20℃; for 1.25h; 4-methyl-7-(naphthalen-2-ylmethoxy)-2H-chromen-2-one (44) VG040-03; Naphthalen-2-ylmethanol (2.0 g, 12.7 mmol) was dissolved in toluene (30 mL) and pyridine (1.02 mL, 12.7 mmol) was added. The solution was cooled to 0 °C. PBr3 (1.19 mL, 12.7 mmol) was added dropwise over 15 min. The mixture was then brought up to room temperature and stirred for 1 h. The mixture was washed with K2CO3 solution and extracted with EtOAc (3 x 30 mL). The EtOAc layer was washed with brine and dried (MgSO4). The solvent was evaporated off in-vacuo to give crude 1- (bromomethyl)naphthalene. This intermediate was used in the following reactions. Sodium ethoxide (169 mg, 2.49 mmol) was added to DMF (5 mL) at 0 0C, and the suspension was stirred for 10 min. 7-hydroxy-4-methylcoumarin (438 mg, 2.49 mmol) was slowly added and resulting mixture was stirred at this temp for 0.5 h, then allowed to reach room temp. To this mixture 1-(bromomethyl)naphthalene (500 mg, 2.26 mmol) was added portionwise. Resulting reaction mixture was stirred at room temperature for 16 h. DMF was evaporated off in-vacuo and the residue was taken up in EtOAc, and washed with brine (2 x 50 mL), water (2 x 50 mL) and 1 M NaOH (2 x 30 mL). The organic layer was dried (MgSO4) and product was purified by flash chromatography, eluting with hexane: EtOAc (2: 1 ) to give 44 (1.44 g, 36%) as a white solid, m/z = 317.12 (M+H), 633.24 (2M+H). H1 NMR (500MHz, CDCI3): δ = 7.93-7.87 (4H, m, ArH), 7.58- 7.52 (4H, m, Ar), 6.97 (1H, t, J = 2.43 Hz, ArH), 6.16 (1 H, s, ArH), 5.32 (2H, s, CH2), 2.41 (3H, s, CH3).
With phosphorus tribromide In dichloromethane at 20℃; for 1h;
With hydrogen bromide at 90℃; 40 [000537j A mixture of Compound 40B (6.00 g, 37.97 mmol) in conc. HBr (200 mL) was stirred at 90 °C overnight. The mixture was diluted with ethyl acetate (200 mL), washed with water and brine, and purified with silica gel column chromatography (ethyl acetate in petroleum ether, 5% v/v) to afford Compound 40C. LCMS (mlz): 221 [M+1], ‘H-NMR (CDC13, 400 MHz) major characteristic peaks: (5(ppm) 4.67 (s, 2H), 7.48-7.52 (m. 3H), 7.80- 7.85 (m, 4H).
Multi-step reaction with 2 steps 1: dipotassium hydrogenphosphate / ethyl acetate / 0.5 h / Milling 2: magnesium bromide ethyl etherate / 1 h / Milling

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[2]Provencher; Wynn; Jones; Krawczyk [Tetrahedron Asymmetry, 1993, vol. 4, # 9, p. 2025 - 2026]
[3]Hussein, Mohanad A.; Nguyen, Thanh Vinh [Chemical Communications, 2019, vol. 55, # 55, p. 7962 - 7965]
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[11]Maya, Ana B. S.; Pérez-Melero, Concepción; Mateo, Carmen; Alonso, Dulce; Fernández, José Luis; Gajate, Consuelo; Mollinedo, Faustino; Peláez, Rafael; Caballero, Esther; Medarde, Manuel [Journal of Medicinal Chemistry, 2005, vol. 48, # 2, p. 556 - 568]
[12]Current Patent Assignee: UNIVERSITY OF HAWAI&apos;I - US6680311, 2004, B1 Location in patent: Page/Page column 150
[13]Current Patent Assignee: UNIVERSITY OF DUNDEE - WO2010/125350, 2010, A1 Location in patent: Page/Page column 54-55
[14]Tummatorn, Jumreang; Thongsornkleeb, Charnsak; Ruchirawat, Somsak; Gettongsong, Tanita [Organic and Biomolecular Chemistry, 2013, vol. 11, # 9, p. 1463 - 1467]
[15]Current Patent Assignee: BIOMARIN PHARMACEUTICAL INC - WO2015/65937, 2015, A1 Location in patent: Paragraph 000537
[16]Dalidovich, Tatsiana; Nallaparaju, Jagadeesh Varma; Shalima, Tatsiana; Aav, Riina; Kananovich, Dzmitry G. [ChemSusChem, 2022, vol. 15, # 3]
  • 3
  • [ 1592-38-7 ]
  • [ 2506-41-4 ]
YieldReaction ConditionsOperation in experiment
93% With 1-methyl-pyrrolidin-2-one; benzenesulfonyl chloride; In 1,2-dichloro-ethane; at 80℃; for 1.5h; General procedure: In a round-bottom flask, benzylic alcohol 1a (10 mmol, 2.0 equiv.), benzenesulfonyl chloride 2a (13 mmol, 1.3 equiv.) and NMP (2.5 equiv.). Then, DCE (3 mL) were added. The mixture was stirred at 80 C for 1.5 h. After completion of the reaction (monitoredby TLC), water (10 mL) was added and the mixture was extracted with ethyl acetate (3*10 mL). The combined organic phase was dried over anhydrous Na2SO4, filtered, and evaporated under reduced pressure. The crude product was purified by flash chromatography on silica gel to give the desired alkyl chlorides 3.
With thionyl chloride; In dichloromethane; toluene; Step A 2-Chloromethyl-naphthalene To 1.26 mol of naphth-2-yl-methanol in 1.5 liters of toluene there are slowly added 3.8 mol of thionyl chloride. The mixture is then heated at reflux for two hours. After cooling, the solvent is evaporated off. The crude product is taken up in toluene twice and evaporated. The oil obtained is taken up in dichloromethane, washed and dried. After filtering and evaporating, the oil obtained is distilled to yield the expected product.
  • 4
  • [ 2459-25-8 ]
  • [ 1592-38-7 ]
YieldReaction ConditionsOperation in experiment
98% Stage #1: methyl naphthalene-2-carboxylate With 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane; lithium tert-butoxide In tetrahydrofuran at 100℃; for 24h; Inert atmosphere; Stage #2: With methanol; sodium hydroxide In tetrahydrofuran at 20℃; Inert atmosphere; 5 The preparation of 2-naphthalenemethanol, the structural formula is as follows: Under the protection of nitrogen, the raw material methyl 2-naphthoate (1 mmol) (1 mmol) and pinacol borane (2.5 mmol) were added, the catalyst LiOtBu (0.05mol) and the solvent tetrahydrofuran (1.0mL) were reacted at 100°C for 24h, subsequently, 2 mol/L NaOH/MeOH solution (ie, 2 mol of sodium hydroxide per liter of methanol) was added, and the mixture was stirred at room temperature overnight, and the product separation yield was 98%.
97% With dimethylsulfide borane complex In 2-methyltetrahydrofuran at 90℃; for 0.333333h; Inert atmosphere; Flow reactor;
91% With 2-(Aminomethyl)pyridine; 1,3-bis-(diphenylphosphino)propane; potassium <i>tert</i>-butylate; hydrogen In 2-methyltetrahydrofuran at 50℃; for 16h; Autoclave;
91% With 2-(Aminomethyl)pyridine; RuCl2(norbornadiene)(pyridine); 1,3-bis-(diphenylphosphino)propane; potassium <i>tert</i>-butylate; hydrogen In 2-methyltetrahydrofuran at 50℃; for 16h; Autoclave;
88% With hydrogen; C28H25BrMnN2O2P; lithium tert-butoxide In propan-1-ol at 100℃; for 5h; Autoclave;
87% With C15H29MnNO3P2(1+)*Br(1-); potassium <i>tert</i>-butylate; hydrogen In 1,4-dioxane at 110℃; for 24h; Inert atmosphere; Autoclave;
87% With C33H29FeMnN2O3P(1+)*Br(1-); potassium <i>tert</i>-butylate; hydrogen In isopropyl alcohol at 75℃; Autoclave;
With lithium aluminium tetrahydride; diethyl ether
With lithium aluminium tetrahydride
With C23H29Cl2N2OPRuS; potassium <i>tert</i>-butylate; hydrogen at 50℃; for 16h; Inert atmosphere; Schlenk technique;
76 %Chromat. With dichlorido-bis[(2-diphenylphosphino)ethyl]amine-cobalt(II); hydrogen; sodium methylate In 1,4-dioxane at 120℃; for 48h; Autoclave;
With 1,1,3,3-Tetramethyldisiloxane; potassium <i>tert</i>-butylate In toluene at 110℃; Glovebox; Inert atmosphere; Sealed tube;
96 %Chromat. With [RuCl2(N-heterocyclic carbene)(bis[2-(diphenylphosphino)ethyl]amine)]; potassium <i>tert</i>-butylate; hydrogen In 2-methyltetrahydrofuran at 45℃; for 2.5h; Autoclave;

Reference: [1]Current Patent Assignee: WENZHOU UNIV NEW MATERIAL AND INDUSTRY TECHNOLOGY - CN113860990, 2021, A Location in patent: Paragraph 0049-0054
[2]Ötvös, Sándor B.; Kappe, C. Oliver [ChemSusChem, 2020, vol. 13, # 7, p. 1800 - 1807]
[3]Carpenter, Ian; Fuentes, Jose A.; Clarke, Matthew L.; Eckelmann, Susan C.; Kuntz, Michael T.; France, Marcia B. [Dalton Transactions, 2012, vol. 41, # 34, p. 10136 - 10140,5]
[4]Carpenter, Ian; Eckelmann, Susan C.; Kuntz, Michael T.; Fuentes, Jose A.; France, Marcia B.; Clarke, Matthew L. [Dalton Transactions, 2012, vol. 41, # 34, p. 10136 - 10140]
[5]Li, Xiao-Gen; Li, Fu; Xu, Yue; Xiao, Li-Jun; Xie, Jian-Hua; Zhou, Qi-Lin [Advanced Synthesis and Catalysis, 2022, vol. 364, # 4, p. 744 - 749]
[6]Elangovan, Saravanakumar; Garbe, Marcel; Jiao, Haijun; Spannenberg, Anke; Junge, Kathrin; Beller, Matthias [Angewandte Chemie - International Edition, 2016, vol. 55, # 49, p. 15364 - 15368][Angew. Chem., 2016, # 128, p. 15590 - 15594]
[7]Widegren, Magnus B.; Harkness, Gavin J.; Slawin, Alexandra M. Z.; Cordes, David B.; Clarke, Matthew L. [Angewandte Chemie - International Edition, 2017, vol. 56, # 21, p. 5825 - 5828][Angew. Chem., 2017, vol. 129, p. 5919 - 5922,4]
[8]Dewar; Sampson [Journal of the Chemical Society, 1956, p. 2789,2791]
[9]Yasuhara,A. et al. [Bulletin of the Chemical Society of Japan, 1972, vol. 45, p. 3638 - 3645] Berner, Endre [Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1982, vol. 36, # 8, p. 547 - 549]
[10]Fuentes, José A.; Smith, Samuel M.; Scharbert, M. Theresa; Carpenter, Ian; Cordes, David B.; Slawin, Alexandra M. Z.; Clarke, Matthew L. [Chemistry - A European Journal, 2015, vol. 21, # 30, p. 10851 - 10869]
[11]Junge, Kathrin; Wendt, Bianca; Cingolani, Andrea; Spannenberg, Anke; Wei, Zhihong; Jiao, Haijun; Beller, Matthias [Chemistry - A European Journal, 2018, vol. 24, # 5, p. 1046 - 1052]
[12]Cook, Adam; Prakash, Sekar; Zheng, Yan-Long; Newman, Stephen G. [Journal of the American Chemical Society, 2020, vol. 142, # 18, p. 8109 - 8115]
[13]Shaalan, Youssef; Boulton, Lee; Jamieson, Craig [Organic Process Research and Development, 2020, vol. 24, # 11, p. 2745 - 2751]
  • 5
  • [ 1592-38-7 ]
  • [ 108-24-7 ]
  • [ 35480-23-0 ]
YieldReaction ConditionsOperation in experiment
90% With manganese(II) chloride tetrahydrate In neat (no solvent) at 25℃; for 3.5h; General procedure for acetylation General procedure: To a stirred mixture of alcohol/phenol/thiohenol/amine (1 mmol) and acetic anhydride(1.1 mmol), 0.01 mmol of MnCl24H2O was added at room temperature. The reaction mixture was stirred until alcohol/phenol/thiohenol/amine was consumed, the progress of the reaction was monitored by TLC. The reaction mixture was quenched with saturated aq. NaHCO3 and extracted with ethyl acetate (10mL 3). The organic layer was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude was passed through a small pad of silica gel (eluent: hexane: ethyl acetate) to obtain pure acetates (acetamides were precipitated out/crystallized direct from the reaction mixture) and characterized by 1H NMR and IR spectroscopy. The data was found to be in accord with previously reported acetates. Characterization data and 1H NMR spectra can be found via the “SupplementaryContent” section of this article’s webpage.
With toluene-4-sulfonic acid; benzene
With dmap In triethylamine 0 degC -> r.t., overnight;
With dmap; triethylamine In diethyl ether
With dmap In dichloromethane at 20℃; for 8h;

  • 6
  • [ 66-99-9 ]
  • [ 1592-38-7 ]
YieldReaction ConditionsOperation in experiment
100% With borohydride Ultra resin In methanol at 20℃; for 2h;
99% With {2,3-bis(diisopropylamino)cycloprop-2-en-1-ylium-1-yl}trihydroborate; mesoporous silica In dichloromethane for 1h;
99% With formalin; triethylamine In 1,2-dimethoxyethane at 80℃; for 26h; Schlenk technique; Inert atmosphere; chemoselective reaction;
98% With sodium tetrahydridoborate In ethanol at 0℃; for 0.166667h;
98% With sodium tetrahydridoborate; Dowex1-x8 In tetrahydrofuran at 20℃; for 1h;
98% With sodium tetrahydridoborate In methanol at 0 - 20℃; for 1h; Inert atmosphere; 2 4.2 Experimental procedure and spectroscopic data for 2-naphthylmethanol (6) Sodium borohydride (500 mg, 13.1 mmol) was added in small portions to a stirred solution of 2-naphthaldehyde (1 g, 6.4 mmol) in dry methanol (25 mL) at 0 °C. The resulting mixture was allowed to come to room temperature and then stirred for 1 h. The solvent was removed under vacuum and the resulting solid was washed with water and dried to give 950 mg of pure 2-naphthylmethanol (6) as a white solid in 98% yield. m.p = 79-81 °C; 1H NMR (300 MHz, CDCl3): δ (ppm): 1.81 (s, 1H, OH); 4.85 (s, 2H, CH2); 7.48 (m, 3H); 7.82 (m, 4H); 13C NMR (75 MHz, CDCl3): δ (ppm): 64.94 (CH2); 124.61 (CH); 124.91 (CH); 125.34 (CH); 125.63 (CH); 127.18 (CH); 127.36 (CH); 127.79 (CH); 132.53 (C); 132.97 (C); 137.90 (C).
98% Stage #1: β-naphthaldehyde With 1-Methylpyrrolidine; 2-chloro-5-fluorophenylboronic acid; phenylsilane at 20℃; for 16h; Inert atmosphere; Stage #2: With sodium hydroxide In lithium hydroxide monohydrate at 20℃; for 2h; chemoselective reaction;
97% Stage #1: β-naphthaldehyde With phenylsilane; C24H40NiO2S In N,N-dimethyl-formamide at 70℃; for 16h; Schlenk technique; Stage #2: With sodium hydroxide In lithium hydroxide monohydrate 2.2 General procedure for catalytic reactions General procedure: Aldehyde (10mmol) was mixed with silane (12mmol) in a 10mL flame-dried Schlenk flask. Solvent (6mL) containing the nickel complex (0.02mmol) was then added. The reaction mixture was stirred at 70°C and the reaction was monitored by using GC-MS. The reaction was stopped after a period of time or after aldehyde was completely consumed. The solvent was removed under vacuum and the resultant residue was treated with a 10wt% of aqueous sodium hydroxide solution (10mL). The aqueous solution was extracted with diethyl ether for three times, dried over anhydrous Na2SO4, and concentrated under vacuum. The desired alcohol was further purified by flash column chromatography on silica gel using petroleum ether/EtOAc as the eluent. Conversions were calculated based on the GC analysis. The characterization data of the isolated alcohol products are provided in Appendix A. The NMR spectra were in good agreement with those reported in the literature [37,49-54].
96% With (1,4-diazabicyclo{2.2.2}-octane)zinc(II) tetrahydoborate In tetrahydrofuran for 1.7h; Ambient temperature;
96.5% With sodium tetrahydridoborate In ethanol for 5h;
95% With [Ir(2,2':6',2'’-terpyridine)(1,10-phenanthroline)Cl](PF6)2; anhydrous sodium formate In ethanol; lithium hydroxide monohydrate at 100℃; for 0.25h; Microwave irradiation; chemoselective reaction; A typical procedure for TH reaction: General procedure: An aldehyde (1 mmol),sodium formate (4.5 eq), and catalyst (0.2 mol%) were taken in70% ethanol in water (4 mL) in a microwave vial and vortexed togenerate a homogenous solution. The mixture was heated in MWat 100 °C using 150W of irradiation. Reaction progress was monitored by TLC. If complete conversion took place, the reaction colorturns to emerald green (color disappears after sometime) from paleyellow, and byproduct Na2CO3 precipitates. The Na2CO3 solid wasremoved by decanting the supernatant. The solid was washed withethyl acetate (20 mL). The combined decanted solution waswashed with water (5.0 mL), followed by brine solution (5.0 mL),dried over Na2SO4, filtered, and evaporated to dryness to affordthe desired alcohol as a pale-yellow liquid or off-white solid.
95% With H2SiEt2 In benzene at 25℃; for 0.0166667h;
95% With [Cp*Ir(2,2'-bpyO)(OH)][Na]; hydrogen In lithium hydroxide monohydrate at 30℃; for 12h; Green chemistry; 4.1. General procedure for catalytic hydrogenation of ketones,aldehydes or unsaturated aldehydes General procedure: To an oven-dried 5 mL round-bottom flask were added ketonesor aldehydes or unsaturated aldehydes (1 mmol), cat. 6 (5.5 mg,1 mol %) and H2O (1 mL). Next, vacuum was applied to the flask followedby filling with H2 gas and keeping the flask attached to a balloonfilled with H2 gas. The mixture was heated at 30 °C for 12 h.After completion of the reaction, the mixture was extracted withethyl acetate (5 mL x 3). Then, the ethyl acetate layers were combined, dried with anhydrous sodium sulfate, filtered, and concentratedby evaporation under reduced pressure. The alcohols wereisolated and purified by filtering a hexanes/ethyl acetate (8:1)solution of the crude product through a pad of silica gel. Thenthe solvent was removed under reduced pressure to afford the correspondingproducts. The purity of alcohol products was assessedusing 1H NMR spectroscopy.
93% With bis-tri-n-butylstannane In methanol; diethyl ether for 4h; Heating;
93% With sodium tetrahydridoborate In ethanol at 40℃; for 16h;
93% Stage #1: β-naphthaldehyde With PMHS; ferrous acetate; tricyclohexylphosphine In tetrahydrofuran at 65℃; for 16h; Stage #2: With Sodium hydrogenocarbonate In tetrahydrofuran; methanol at 0 - 20℃; Further stages.;
93% With (1,3-dimethyl-1H-imidazol-3-ium-2-yl)trihydroborate; glacial acetic acid In ethyl acetate at 20℃; for 24h;
93% With C18H32BrFeNO3P2; anhydrous sodium formate In methanol; dodecane at 40℃; for 6h; Inert atmosphere; chemoselective reaction;
93% Stage #1: β-naphthaldehyde With phenylsilane; C74H74Mn2N6P4 at 25℃; for 0.0333333h; Glovebox; Inert atmosphere; Stage #2: With sodium hydroxide In lithium hydroxide monohydrate at 25℃; for 2h; Glovebox; Inert atmosphere;
93% With hydrogen; C27H27ClIrNO In methanol at 60℃; for 6h; Autoclave;
92% With sodium tetrahydridoborate In methanol at 0 - 20℃; for 1h;
91% With hantzsch ester; tris[3,5-bis(trifluoromethyl)phenyl]borane In 1,4-dioxane at 25℃; for 12h; Glovebox; General procedure for the hydrogenation reaction General procedure: In a glovebox, aldehydes (0.25 mmol) and the Hantzsch ester 1 (95 mg, 0.38 mmol) were added to asolution of tris[3,5-bis(trifluoromethy)phenyl]borane (9) (8.1 mg, 12.5 μmol) in 1 mL of anhydrous1,4-dioxane. The reaction mixture was stirred at 25 or 100 C for 12 h. An internal standard (biphenylor mesitylene) was added to the reaction mixture and filtrated through a cotton plug. The resultingsolution was analyzed with gas chromatography.
90% With sodium tetrahydridoborate; zinc(II) iodide In 1,2-dichloro-ethane at 83℃; for 48h;
90% With 4-aza-N-benzyl-bicyclo<2,2,2>octyl ammonium borohydride In <i>tert</i>-butyl alcohol for 0.25h;
90% With sodium tetrahydridoborate; lithium perchlorate In acetonitrile for 0.333333h;
90% With 1,4-diaza-bicyclo[2.2.2]octane; anhydrous silver tetrafluoroborate; C15H4BClCoF18N6; hydrogen In tetrahydrofuran at 60℃; for 10h;
90% With isopropanol; potassium hydroxide at 80℃; for 4h; Sealed tube;
89% With methanol; sodium tetrahydridoborate at 0 - 20℃; Inert atmosphere;
88% With alumina-supported potassium hydroxide; isopropanol for 0.233333h; microwave irradiation;
88% With sodium tetrahydridoborate In methanol at 0 - 20℃; for 2h;
87% With (1,3-dimethyl-1H-imidazol-3-ium-2-yl)trihydroborate; mesoporous silica In ethyl acetate at 20℃; for 8h;
87% Stage #1: β-naphthaldehyde With phenylsilane; (Ph<SUB>2</SUB>PPrPDI)Mn In diethyl ether at 25℃; for 0.0333333h; Glovebox; Inert atmosphere; Stage #2: With sodium hydroxide In diethyl ether; lithium hydroxide monohydrate at 25℃; for 2h; Glovebox;
86% With ammonia hydrochloride; zinc In tetrahydrofuran; lithium hydroxide monohydrate at 20℃; for 0.333333h;
86% With Zinc acetate; 4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Sealed tube; 1 Example 1 2-Naphthylcarbinol with the following structural formula was synthesized. Add 0.0004g (0.002mmol) of zinc acetate and 0.0312g (0.2mmol) of 2-naphthaldehyde to a 25mL high pressure reaction tube. Use a double-row tube for three fillings and three discharges, add 44 μL (0.3 mmol) HBpin and 2.0 mL THF in sequence under nitrogen flow, and stir the reaction at room temperature for 1 hour after sealing the tube. The reaction was quenched by adding 10 mL of saturated aqueous ammonium chloride solution, extracted with ethyl acetate (10 mL each time, 3 times), the extracts were combined, dried by adding anhydrous sodium sulfate. Using petroleum ether: ethyl acetate volume ratio of 5:1 mixed solution as developing solvent, the product was separated by column chromatography to obtain 2-naphthalene methanol as a white solid with a yield of 86%.
85% With potassium fluoride on basic alumina; formalin for 0.133333h; microwave irradiation;
82% With Butane-1,4-diol; potassium-t-butoxide In tetrahydrofuran for 48h; Heating;
82% With Sodium Tris(1,1,1,3,3,3-hexafluoroisopropoxy)borohydride In tetrahydrofuran; hexafluoropropan-2-ol at 0℃; for 0.5h; chemoselective reaction;
82% Stage #1: β-naphthaldehyde With (1R,2S)-N-benzylephedrine; diethylzinc(II) In toluene Inert atmosphere; Stage #2: With ammonia hydrochloride In toluene Inert atmosphere;
82% With H<SUB>2</SUB>Ru(CO)(PPh<SUB>3</SUB>)<SUB>3</SUB>; Butane-1,4-diol; potassium-t-butoxide; bis[2-(diphenylphosphino)phenyl] ether In toluene for 48h; Inert atmosphere; Reflux;
82% With C16H9BrMnN3O4; potassium-t-butoxide In isopropanol at 85℃; for 24h; Inert atmosphere; Schlenk technique;
79% With bis[chlorido(η2,η2-cycloocta-1,5-diene)rhodium(I)]; tetrahydroxydiborane; lithium hydroxide monohydrate; triethylamine In ethanol at 30℃; for 12h; Schlenk technique; Inert atmosphere;
76% Stage #1: β-naphthaldehyde With cyclopentadienyl iron(II) dicarbonyl dimer; methyldiethoxysilane at 100℃; for 24h; Stage #2: With lithium hydroxide monohydrate; sodium hydroxide In methanol
75% With bis(tricyclohexylphosphine)benzylidene ruthenium (IV) dichloride; potassium hydroxide In 1,4-dioxane at 80℃; for 20h;
75% With strontium diisopropoxide; isopropanol for 4h; Heating;
75% Stage #1: β-naphthaldehyde With phenylsilane; C24H45BN2P2PtS In hexane at 65℃; for 1h; Inert atmosphere; Sealed tube; Stage #2: With sodium hydroxide In hexane; lithium hydroxide monohydrate at 20℃; for 2h; Inert atmosphere; Sealed tube;
73% With hydrogen In ethanol; lithium hydroxide monohydrate at 40℃; for 0.00611111h; Flow reactor; Green chemistry; chemoselective reaction;
71% With manganese powder; lithium hydroxide monohydrate; 2,4,6-trimethylpyridinium chloride In tetrahydrofuran at 20℃;
67% With lithium tert-butylate In isopropanol at 20℃; for 36h; UV-irradiation;
65% With Triethoxysilane; zinc In tetrahydrofuran for 39h; Inert atmosphere; Reflux; General procedure for reduction of carbonyl compounds toalcohols General procedure: Into a 25 mL round-bottomed flask was placed 0.065 g of active zinc (Zn*, 1.0 mmol) in 7 mL of THF under an argon atmosphere. Next, 0.37 mL of triethoxysilane (0.328 g, 2.0 mmol) and 0.19 mL of 3-thiophenecarboxaldehyde (0.224 g, 2.0 mmol) was cannulated at room temperature. The resulting mixture was stirred for 39 h at refluxing temperature. The reaction mixture was cooled down to room temperature. Quenched with 6 M HCl solution, then extracted with diethyl ether (6 × 35 mL).Combined organic layers were washed with NaHCO3 solution and brine, then dried over anhydrous Na2SO4. Purificationby flash column chromatography on silica gel (35% ethyl acetate/90% hexanes) afforded 0.137 g of thiophen-3-yl-methanol (2m) in 60 % isolated yield as an orange liquid;
With dimethyl zinc; sodium hydride In tetrahydrofuran; hexane at -20℃; for 6h; relative reactivity (vs benzophenone);
With ethanol; iron(III) chloride; platinum Hydrogenation;
With methanol; sodium tetrahydridoborate
With sodium tetrahydridoborate In ethanol; lithium hydroxide monohydrate at 20℃;
With sodium tetrahydridoborate In methanol at 20℃;
With sodium tetrahydridoborate
99 % Chromat. With sodium tetrahydridoborate; benzoic acid for 0.666667h;
With anhydrous sodium formate; N-(2-amino-ethyl)-4-methyl-benzenesulphonamide at 80℃; for 1.5h;
With sodium tetrahydridoborate In ethanol at 50℃; for 3h;
With C55H48As2N3O3RuS; isopropanol; potassium hydroxide for 0.5h; Reflux;
32 %Chromat. With titanium(IV) dioxide; isopropanol for 1h; Inert atmosphere; UV-irradiation;
Multi-step reaction with 2 steps 1: C24H50FeO2P4 / tetrahydrofuran / 3 h / 65 °C / Inert atmosphere 2: lithium hydroxide monohydrate; sodium hydroxide / tetrahydrofuran; methanol / 48 h / 50 °C
With cytochrome P450BM-3 F87A/T268A variant; NADPH at 37℃; aq. phosphate buffer; Enzymatic reaction;
With sodium tetrahydridoborate; lithium hydroxide monohydrate In acetonitrile
51 %Chromat. With sodium hydroxide In isopropanol at 82℃; for 0.75h; 2.3. Transfer hydrogenation of carbonyl compounds General procedure: In a typical procedure, a 5 mg (0.77 mol%) of RuO2/MWCNT and 80 mg (2 mmol) of NaOH were stirred with 5 mL of i-PrOH taken in an ace pressure tube equipped with a stirring bar. Then the substrate (1 mmol) was added to the stirring solution and then the mixture was heated at 82°C. The completion of the reaction was monitored by GC. After the reaction, the catalyst was separated out from the reaction mixture by simple centrifugation and the products and unconverted reactants were analyzed by GC without any purification. Selectivity of the product for each reaction was alsocalculated. Finally, the separated RuO2/MWCNT was washed well with diethyl ether followed by drying in an oven at 60°C for 5 h and it was reused for the subsequent transfer hydrogenation of carbonyl compounds to investigate the reusability of the RuO2/MWCNT.
95 %Spectr. With Aeroxide (Evonik) P25 TiO2, consisting of a 3:1 anatase/rutile mixture In methanol; acetonitrile at 20℃; for 20h; Schlenk technique; Inert atmosphere; UV-irradiation;
81 %Chromat. With formalin; triscarbonyl-(2,4-bis(trimethylsilyl)bicyclo[3.3.0]nona-1,4-dien-3-one)iron; lithium hydroxide monohydrate; anhydrous sodium carbonate In dimethyl sulfoxide at 120℃; for 24h; Inert atmosphere; Sealed tube; Reduction of benzaldehyde to benzylalcohol General procedure: Knölker iron complex 2a (3 mol %,12.6 mg), paraformaldehyde (300 mg, 10 mmol), and Na2CO3 (106 mg, 1 mmol,1.0 equiv) and a stirring bar were charged in a pressure tube and flushed withargon. DMSO (1.0 mL), degassed water (1.0 mL), and benzaldehyde (1 mmol)were added under an argon atmosphere to the pressure tube with a syringe.The pressure tube was placed in oil and heated at 120 C for 24 h, then cooledto room temperature. The reaction mixture was neutralized with HCl (1M) andstirred for 30 min. After extraction with EtOAc for 3 times, the combinedorganic layers were dried over MgSO4. The crude product was purified bycolumn chromatography (Heptane/EtOAc: 70:30). The reaction was cooled toroom temperature and hexadecane (100 lL) was added as a GC internalstandard.
Multi-step reaction with 2 steps 1: C59H80FeO2P4 / tetrahydrofuran / 65 °C 2: sodium hydroxide; lithium hydroxide monohydrate / methanol
With sodium tetrahydridoborate; ethanol at 20℃; for 2h; 40 [000536j To a solution of Compound 40A (14.10 g, 90.38 mmol) in EtOH (100 mL) was added NaBH4 (3.43 g, 90.83 mmol). The mixture was stirred at room temperature for 2 h. The mixture was diluted with ethyl acetate (300 mL), washed with water and brine, dried with anhydrous Na2SO4, and evaporated to render Compound 40B. LCMS (mlz): 159 [M+1]’H-NMR (CDC13, 400 MHz) major characteristic peaks: (5(ppm) 4.89 (s, 2H), 7.46- 7.49 (m. 3H), 7.8 1-7.86 (m, 4H).
With lithium aluminium hydride In tetrahydrofuran at 0℃; for 0.5h;
Multi-step reaction with 2 steps 1: dichloro(p-cymene)ruthenium(II) dimer / benzene / 4 h / 20 °C / Inert atmosphere; Glovebox 2: hydrogenchloride; lithium hydroxide monohydrate / methanol / 1 h / Reflux
97 %Spectr. With 1-hydrosilatrane; sodium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.5h;
With sodium tetrahydridoborate In methanol at 20℃; for 1h; Inert atmosphere; 2.1 General procedure for the synthesis of alcohols: GP-1 General procedure: The carbonyl compound (1 mmol) and NaBH4 (2 mmol) were taken in a two-neck round bottomed flask and flashed with nitrogen gas. Then 5 mL of methanol was added to it and stirred at room temperature for 1h. After completion of the reaction, methanol was evaporated under reduced pressure and then the reaction mixture was diluted with saturated ammonium chloride solution and extracted with ethyl acetate (3 x 20 mL). The combined organic layer was washed with brine, dried over anhydrous Na2SO4, evaporated under reduced pressure. Then the crude product was purified by column chromatography using silica gel (60-120 mesh) and hexane/EtOAc as eluent.
With sodium tetrahydridoborate Inert atmosphere;
Multi-step reaction with 2 steps 1: C27H44AlN3 / 0.33 h / 20 °C / Inert atmosphere; Glovebox 2: mesoporous silica / Inert atmosphere; Heating
With sodium tetrahydridoborate In ethanol at 0 - 20℃; Inert atmosphere;
With sodium tetrahydridoborate at 0℃;
50 %Spectr. With 2,2'-bi(1,3,6,2-dioxazaborocane); lithium hydroxide monohydrate at 20℃; for 18h; Inert atmosphere; Sealed tube;
With sodium tetrahydridoborate In methanol
Multi-step reaction with 2 steps 1: Nd(O(2,6-tBu<SUB>2</SUB>-4-MeC<SUB>6</SUB>H<SUB>2</SUB>))<SUB>3</SUB>(THF)<SUB>2</SUB> / tetrahydrofuran / 0.25 h / 25 °C 2: hydrogenchloride / lithium hydroxide monohydrate
With methanol; sodium tetrahydridoborate for 1h; Cooling with ice; 5.1.3. Phenylmethanol (8a) General procedure: To a solution of compound 7a (1.06 g, 10 mmol) in methanol(10 mL) was added NaBH4 (0.57 g, 15 mmol). After stirring for 1 hwhile cooled with an ice-water bath, methanol was evaporatedand the residue was dissolved in EtOAc (100 mL). The organic layerwas washed with water (3 100 mL) and brine (3 100 mL), anddried over MgSO4 overnight. EtOAc was evaporated to give 8a ascolorless oil (2.01 g, yield: 94%). ESI-MS m/z 109.4 [M+H]+. The crude product was used directly in the next reaction without furtherpurification. Compounds 8b-8u, 8aa-8ff, 10v-10w, 17a-17b and 22a-22hwere prepared using the same procedure described above
Multi-step reaction with 2 steps 1: C22H36CoNO4P2 / tetrahydrofuran / 12 h / 50 °C / Schlenk technique; Inert atmosphere 2: sodium hydroxide / lithium hydroxide monohydrate / 24 h / 50 °C / Schlenk technique; Inert atmosphere
With sodium tetrahydridoborate In methanol at 0℃; Inert atmosphere;
With sodium tetrahydridoborate
Multi-step reaction with 2 steps 1: n-butyllithium / tetrahydrofuran; hexane / 0.08 h / 0 °C / Inert atmosphere 2: sodium hydroxide / tetrahydrofuran; hexane; lithium hydroxide monohydrate / 0.5 h / 0 °C
> 99 %Chromat. With borane-ammonia complex In methanol; lithium hydroxide monohydrate at 20℃; for 0.0333333h; Typical procedure for the hydrogenation of ketones and aldehydes General procedure: mpg-C3N4/Pd (4 mg) and the ketone or aldehyde (0.35 mmol)were suspended in methanol/water mixture (2 mL, 1:1) in apressure tube. Subsequently, AB (0.75 mmol) was addedand the solution was magnetically stirred for 2 (for aldehydes)or 5 min (for ketones) at room temperature. Aftercompletion of the reaction, the catalyst was filtered andwashed with methanol for further use. The solvent wasremoved under the reduced pressure. The yield of each alcoholwas determined by gas chromatography-mass spectrometry(GC-MS).
Multi-step reaction with 2 steps 1: [2,6-(iPr2PO)2C6H3]PtH / toluene / 2 h / 60 °C / Inert atmosphere; Schlenk technique 2: sodium hydroxide / lithium hydroxide monohydrate
With sodium tetrahydridoborate In methanol at 0 - 20℃; Inert atmosphere; General Procedure A General procedure: To a solution of the aldehyde (1.0 equiv) in MeOH (0.50 M) at 0 C wasadded NaBH4 (2.4 equiv) in 5 parts. The resulting mixture was stirred at room temperature untilthe reaction was judged to have reached completion by TLC. A saturated aqueous solution ofNH4Cl was then added to the reaction mixture, the layers were separated and the aqueous phasewas extracted with EtOAc (3x). The combined organic layers were washed with brine (1x), driedover MgSO4 and concentrated under reduced pressure. The crude residue was directly carriedonto the next step and purified if necessary
66 %Chromat. With C32H27N6ORu(1+)*NO3(1-); isopropanol; potassium hydroxide at 85℃; for 12h; General procedure for the catalytic transfer-hydrogenationreactions: General procedure: In a typical run, an oven-dried 10 ml round-bottomed flaskwas charged with the aldehyde/ketone (1 mmol), a knownmol percent of the catalyst, and KOH (0.1 mmol) dissolvedin 2-propanol (5 ml). The flask was placed in a preheated oilbath at the required temperature. After the specified time,the flask was removed from the oil bath and water (20 ml)was added, neutralized with 1(M) HCl, and extracted withdiethyl ether (4-10 ml). The combined organic layers werewashed with water (3-10 ml), dried with anhydrous Na2SO4,and filtered. Diethyl ether was removed under vacuum andthe residue obtained dissolved in hexane and analyzed byGC-MS.
Multi-step reaction with 2 steps 1: lithium bromide / tetrahydrofuran / 1 h / 24 - 25 °C / Inert atmosphere 2: sodium hydroxide; lithium hydroxide monohydrate / tetrahydrofuran; lithium hydroxide monohydrate / 0.5 h / 20 °C
Multi-step reaction with 2 steps 1: potassium hydroxide; triethyl borane / tetrahydrofuran / 4 h / 25 °C / Inert atmosphere; Schlenk technique; Sealed tube 2: sodium hydroxide; lithium hydroxide monohydrate / tetrahydrofuran / 1 h / 25 °C / Inert atmosphere; Schlenk technique; Sealed tube
With sodium tetrahydridoborate
45 %Chromat. With potassium-t-butoxide; hydrogen; tetracarbonyl(2-(diphenylphosphino)-ethylamine)chromium(0) In diethylene glycol dimethyl ether at 120℃; for 20h; Autoclave;
With methanol; sodium tetrahydridoborate at 0 - 20℃; Inert atmosphere; Sealed tube;
Multi-step reaction with 2 steps 1: P(C6H5)2CH2N2BHC6H4CH2P(C6H5)2; diiron nonacarbonyl / neat (no solvent) / 65 °C / Schlenk technique; Inert atmosphere 2: sodium hydroxide / lithium hydroxide monohydrate / Schlenk technique; Inert atmosphere
Multi-step reaction with 2 steps 1: tetrahydrofuran / 0.08 h / 20 °C 2: lithium hydroxide monohydrate
With sodium tetrahydridoborate In methanol at 0 - 20℃; for 3h; Inert atmosphere;

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[82]Michel, Nicholas W. M.; Jeanneret, Alexandria D. M.; Kim, Hyehwang; Rousseaux, Sophie A. L. [Journal of Organic Chemistry, 2018, vol. 83, # 19, p. 11860 - 11872]
[83]Suga, Takuya; Ukaji, Yutaka [Organic Letters, 2018, vol. 20, # 24, p. 7846 - 7850]
[84]Yang, Su Jin; Jaladi, Ashok Kumar; Kim, Jea Ho; Gundeti, Shankaraiah; An, Duk Keun [Bulletin of the Korean Chemical Society, 2019, vol. 40, # 1, p. 34 - 38]
[85]Nişancı, Bilal; Dağalan, Ziya [Journal of Chemical Research, 2020, vol. 44, # 1-2, p. 14 - 19]
[86]Chang, Jiarui; Fang, Fei; Zhang, Jie; Chen, Xuenian [Advanced Synthesis and Catalysis, 2020, vol. 362, # 13, p. 2709 - 2715]
[87]Patel, Purvish; Rousseaux, Sophie A. L. [Synlett, 2020, vol. 31, # 5, p. 492 - 496]
[88]Kumar, Rohit; Paul, Piyali; Bhattacharya, Samaresh [Journal of the Indian Chemical Society, 2018, vol. 95, # 7, p. 721 - 728]
[89]An, Duk Keun; Choi, Hyeon Seong; Hwang, Hyonseok; Kim, Hanbi; Lee, Ji Hye; Shin, Hye Lim; Yi, Jaeeun [Bulletin of the Korean Chemical Society, 2020, vol. 41, # 10, p. 1009 - 1018]
[90]Li, Jinshan; Wang, Jiali; Yang, Jianguo; Yao, Wubing; Zhong, Aiguo [Organic Letters, 2020, vol. 22, # 20, p. 8086 - 8090]
[91]Onodera, Gen; Kumagae, Hidenobu; Nakamura, Daiki; Hayasaki, Takuto; Fukuda, Tsutomu; Kimura, Masanari [Tetrahedron Letters, 2020, vol. 61, # 47]
[92]Faust, Kirill; Topf, Christoph; Vielhaber, Thomas [Organometallics, 2020, vol. 39, # 24, p. 4535 - 4543]
[93]Liu, Zhi-Yun; Cook, Silas P. [Organic Letters, 2021, vol. 23, # 3, p. 808 - 813]
[94]Fang, Fei; Chang, Jiarui; Zhang, Jie; Chen, Xuenian [Catalysis Letters, 2021, vol. 151, # 12, p. 3509 - 3515]
[95]Wang, Jin; Guo, Yu; Li, Shouhu; Chen, Xuenian [Synlett, 2021, vol. 32, # 11, p. 1104 - 1108]
[96]Wang, Wei; Yao, Ken; Wu, Fan [Synlett, 2022, vol. 33, # 4, p. 361 - 366]
  • 7
  • [ 1592-38-7 ]
  • [ 24515-49-9 ]
YieldReaction ConditionsOperation in experiment
98% With chloro-trimethyl-silane; sodium iodide In acetonitrile for 2h; Ambient temperature;
78% Stage #1: 2-Naphthalenemethanol With sodium tetrahydroborate In 1,4-dioxane at 80℃; for 0.5h; Inert atmosphere; Stage #2: With iodine In 1,4-dioxane at 60℃; for 24h; Inert atmosphere; Sealed tube; 14 Example 14: 2-Iodomethylnaphthalene (R=Ph in structural formula II) In a 25 mL reactor under nitrogen, add sodium borohydride (19.0 mg, 0.5 mmol), 2-naphthalene methanol (79.1 mg, 0.5 mmol) and 1,4-dioxane (1 mL) in sequence, and heat to After keeping at 80°C for 0.5 hours, it was cooled to room temperature. After adding iodine granules (126.9mg, 0.5mmol), the reactor was sealed and reacted at 60°C for 24 hours. After the reaction system was cooled to room temperature, 5 mL of water and 5 mL of ethyl acetate were added dropwise and stirred for 10 min, and then extracted twice with 10 mL of ethyl acetate, and the organic phases were combined. Dry with anhydrous sodium sulfate for 0.5h, filter, and rotatory-evaporate the organic phase to obtain a crude product. The crude product is separated by 200-300 mesh neutral silica gel column adsorption phase column chromatography using petroleum ether as the eluent to obtain 104.5 mg of white solid product 2-iodomethylnaphthalene with a purity greater than 99%, and the separation yield is 78%.
With hydrogen iodide In diethyl ether 1.) -30 deg C, 5 min; 2.) room temp., 0.5 h; Yield given;
Stage #1: 2-Naphthalenemethanol With boron trifluoride diethyl etherate; cesium iodide In acetonitrile at 20℃; for 0.5h; Inert atmosphere; Stage #2: With N-ethyl-N,N-diisopropylamine In acetonitrile Inert atmosphere;
Multi-step reaction with 2 steps 1: dipotassium hydrogenphosphate / ethyl acetate / 0.5 h / Milling 2: potassium iodide / 1 h / Milling

  • 9
  • [ 1592-38-7 ]
  • [ 91-20-3 ]
  • [ 66-99-9 ]
YieldReaction ConditionsOperation in experiment
1: 61% 2: 20% With chlorobis(cyclooctene)-iridium(I) dimer; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In 1,3,5-trimethyl-benzene at 164℃; for 8h;
1: 5% 2: 42% With sodium hydroxide; di(rhodium)tetracarbonyl dichloride; N-benzyl-N,N,N-triethylammonium chloride In benzene at 55℃; for 4h;
With oxygen In toluene at 90℃; for 10h; 2.3.1 Aerobic alcohol oxidation The oxidation reaction of alcohol was performed according to the following sequence: PdOSNP (40mg, Pd=3.3mol% of substrate) with toluene (2mL) and alcohol (0.2mmol) was charged in the glass tube reactor. The mixture was stirred at 1000rpm using magnetic stirrer bar under atmospheric pressure of molecular oxygen at 90°C. The conversion and yield were obtained by taking the sample from a mixture at regular intervals and analyzing them with gas chromatography (GC, Younglin GC-6500) and at the end by GC-mass spectroscopy (GC-MS, JEOL GCMS-BU20) to compare with the standard samples. GC analyses were carried out using a flame ionization detector (FID) equipped with a DB-WAX capillary column. GC-MS were recorded at an ionization voltage of 70eV equipped with a DB-WAX capillary column (internal diameter=0.25mm, length=30m).
1: 50 %Spectr. 2: 39 %Spectr. With dodecacarbonyl-triangulo-triruthenium; triphenylphosphine at 177℃; for 16h; Schlenk technique; Inert atmosphere;

  • 10
  • [ 3007-91-8 ]
  • [ 1592-38-7 ]
YieldReaction ConditionsOperation in experiment
79% With sodium tetrahydroborate; <i>N</i>,<i>N</i>-dimethyl-aniline; zinc(II) chloride In tetrahydrofuran for 2h; Heating;
72% With 15-crown-5; (1-(2-(2,3-diisopropyl-1-methylguanidino)ethyl)-3-mesityl-1,3-dihydro-2H-imidazol-2-ylidene)copper(I) chloride; hydrogen; sodium t-butanolate In 1,4-dioxane at 60℃; for 24h; Inert atmosphere; Large scale;
With lithium aluminium tetrahydride
Multi-step reaction with 2 steps 1: lithium tert-butoxide / tetrahydrofuran / 12 h / 0 - 20 °C 2: sodium hydroxide / water / 1 h / 20 °C

  • 11
  • [ 76373-16-5 ]
  • [ 1592-38-7 ]
  • [ 78038-79-6 ]
  • [ 5978-70-1 ]
  • 12
  • [ 108-05-4 ]
  • [ 1592-38-7 ]
  • [ 35480-23-0 ]
YieldReaction ConditionsOperation in experiment
63% With sodium carbonate In acetonitrile at 120℃; for 24h; Schlenk technique; General Procedure for the Synthesis of Aryl Carboxylates General procedure: A mixture of phenol 1 (0.50 mmol), Na2CO3 (10.6 mg, 0.10mmol, 20 mol%), and alkenyl carboxylate (2.0 mmol, 4.0 equiv)in MeCN (3 mL) was added to a Schlenk flask (25 mL) and stirredat r.t. The mixture was stirred at 120 °C until the reaction wasfinished. Then, the solvent was evaporated under reduced pressureand the residue was purified by column chromatography(petroleum ether/ethyl acetate 20:1 to 10:1) to afford theproduct 3.
5% In chloroform at 30℃; for 120h; Pseudomonas cepacia lipase;
  • 13
  • [ 1592-38-7 ]
  • [ 3282-30-2 ]
  • 2,2-dimethylpropanoic acid 2-naphthalenylmethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
100% at 20℃; for 0.0833333h; Neat (no solvent);
90% Stage #1: 2-Naphthalenemethanol With dmap; triethylamine In dichloromethane at 20℃; Inert atmosphere; Stage #2: pivaloyl chloride In dichloromethane at 0℃; for 0.3h; Inert atmosphere;
90% With dmap; triethylamine In dichloromethane at 0 - 20℃; for 0.25h;
90% With dmap; triethylamine In dichloromethane at 0℃; for 0.3h;
90% With dmap In dichloromethane at 24℃; Inert atmosphere;
80% With triethylamine In dichloromethane at 0 - 20℃;
68% With pyridine In tetrahydrofuran at 25℃; for 1h;
With triethylamine In dichloromethane at 20℃;
With triethylamine In dichloromethane at 20℃; Inert atmosphere; Schlenk technique;
With triethylamine In dichloromethane at 0 - 25℃;
With triethylamine In dichloromethane at 20℃; Inert atmosphere; Schlenk technique;
3.96 g With dmap; triethylamine In dichloromethane at 0℃; Inert atmosphere;
With triethylamine In dichloromethane at 0 - 20℃;

Reference: [1]Rao, Ch. Bhujanga; Chinnababu; Venkateswarlu [Journal of Organic Chemistry, 2009, vol. 74, # 22, p. 8856 - 8858]
[2]Xiao, Jing; Chen, Tieqiao; Han, Li-Biao [Organic Letters, 2015, vol. 17, # 4, p. 812 - 815]
[3]Xiao, Jing; Yang, Jia; Chen, Tieqiao; Han, Li-Biao [Chemical Communications, 2016, vol. 52, # 10, p. 2157 - 2160]
[4]Xiao, Jing; Yang, Jia; Chen, Tieqiao; Han, Li-Biao [Advanced Synthesis and Catalysis, 2016, vol. 358, # 5, p. 816 - 819]
[5]Konev, Mikhail O.; Hanna, Luke E.; Jarvo, Elizabeth R. [Angewandte Chemie - International Edition, 2016, vol. 55, # 23, p. 6730 - 6733][Angew. Chem., 2016, vol. 55, # 23, p. 6730 - 6733,4]
[6]Correa, Arkaitz; Leon, Thierry; Martin, Ruben [Journal of the American Chemical Society, 2014, vol. 136, # 3, p. 1062 - 1069]
[7]Li, Weijin; Fox, Marye Anne [Journal of the American Chemical Society, 1996, vol. 118, # 47, p. 11752 - 11758]
[8]Zarate, Cayetana; Martin, Ruben [Journal of the American Chemical Society, 2014, vol. 136, # 6, p. 2236 - 2239]
[9]Yang, Jia; Chen, Tieqiao; Han, Li-Biao [Journal of the American Chemical Society, 2015, vol. 137, # 5, p. 1782 - 1785]
[10]Gu, Yiting; Martín, Rúben [Angewandte Chemie - International Edition, 2017, vol. 56, # 12, p. 3187 - 3190][Angew. Chem., 2017, vol. 129, # 12, p. 3235 - 3238,4]
[11]Xi, Xiaoxiang; Chen, Tieqiao; Zhang, Ji-Shu; Han, Li-Biao [Chemical Communications, 2018, vol. 54, # 12, p. 1521 - 1524]
[12]Michel, Nicholas W. M.; Jeanneret, Alexandria D. M.; Kim, Hyehwang; Rousseaux, Sophie A. L. [Journal of Organic Chemistry, 2018, vol. 83, # 19, p. 11860 - 11872]
[13]Tang, Jinghua; Liu, Liu Leo; Yang, Shangru; Cong, Xuefeng; Luo, Meiming; Zeng, Xiaoming [Journal of the American Chemical Society, 2020, vol. 142, # 17, p. 7715 - 7720]
  • 14
  • [ 1592-38-7 ]
  • [ 201230-82-2 ]
  • [ 581-96-4 ]
YieldReaction ConditionsOperation in experiment
90% With tetrakis(triphenylphosphine) palladium(0); hydrogen iodide In acetone at 90℃; for 42h;
  • 15
  • [ 1592-38-7 ]
  • [ 201230-82-2 ]
  • [ 91-57-6 ]
  • [ 581-96-4 ]
YieldReaction ConditionsOperation in experiment
97% With hydrogen iodide In acetone at 90℃; for 42h;
  • 16
  • [ 10132-07-7 ]
  • [ 1592-38-7 ]
  • 4-amino-6-chloro-2-(2-naphthylmethyloxy)-pyrimidine [ No CAS ]
  • 17
  • [ 52545-13-8 ]
  • [ 1592-38-7 ]
  • C17H17NO3 [ No CAS ]
  • 18
  • [ 1592-38-7 ]
  • [ 613-46-7 ]
YieldReaction ConditionsOperation in experiment
81% With 1,4-diaza-bicyclo[2.2.2]octane; TEMPOL; ammonia; copper(l) chloride; In water; acetonitrile; at 20℃; for 24h; General procedure: To a 25-mL Schlenk tube equipped with a magnetic stirrer, CuCl (0.05 mol, 5 mol%), DABCO (0.10 mol, 10 mol%), 4-HO-TEMPO (0.05 mmol, 5 mol%) were added. Substrates 1 (1 mmol) and NH3 (aq, 25-28%, 3 mmol, 3.0 equiv) in CH3CN (2 mL) were added subsequently. Then the reaction mixture was stirred at room temperature for 24 h in the presence of an air balloon. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water and extracted with ethyl acetate. The organic layer was dried over anhydrous MgSO4. Subsequently, the combined organic layer was concentrated under reduced pressure and the crude product was purified by column chromatography to afford the corresponding products.
74% With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; ammonium acetate; oxygen; nitric acid; acetic acid; at 50℃; under 760.051 Torr; for 12h;Sealed tube; General procedure: 0.5 mmol substrate, 1.5 mmol NH4OAc, 0.15 mmol TEMPO, 2 mL AcOH and 0.15 mmol HNO3 weresuccessively added to a dried 45 mL tube filled with 1atm oxygen. Then the reaction tube was sealed andplaced in a constant-temperature oil bath to perform the reaction for 12 h. Once the reaction time wasreached, the mixture was cooled to room temperature. Then the mixture was alkalized to pH 7-8 with sodiumhydroxide aqueous solution. GC analysis of organic phase provided the GC yields of the products.Subsequently, the crude product from another parallel experiment was purified by column chromatography,and identified by 1H-NMR, 1C-NMR or GC-MS
  • 19
  • [ 1592-38-7 ]
  • [ 2873-29-2 ]
  • [ 647021-58-7 ]
YieldReaction ConditionsOperation in experiment
89% With iron(III) trifluoromethanesulfonate In dichloromethane for 3.5h; Reflux; diastereoselective reaction; 4.2. General procedure for preparation of 2,3-unsaturated O-glycosides General procedure: To a stirred solution of tri-O-acetyl-d-glucal (136 mg, 0.5 mmol) in DCM (5 mL) were added the corresponding alcohol (1.2 equiv) and iron(III) triflate (10 mol %) at ambient temperature. The reaction mixture was refluxed and the extent of the reaction was monitored by TLC analysis. The reaction mixture was diluted with cooled sodium bicarbonate (satd, 20 mL) and extracted with DCM (3×10 mL). The combined organics were dried over anhydrous Na2SO4. The solvent was removed under vacuum. All the products were purified by silica gel column chromatography (hexane/EtOAc=6/1).
81% With boron trifluoride diethyl etherate In dichloromethane at -30 - 20℃;
80% With triflic acid supported on silica gel at 40℃; for 0.166667h; 11 General procedure for preparation of 2,3-unsaturated glycosides General procedure: To a stirred solution of tri-O-acetyl-D-glucal(136mg, 0.5 mmol) and the corresponding alcohol (1.2 eq) in THF (8 mL) were added CF3SO3H-SiO2 (10mol%) at ambient temperature.The mixture was stirred under 40°C for the appropriate amount of time (Table 3), and the extent of the reaction was monitored by TLC analysis.The reaction mixture was diluted with cooled sodium bicarbonate (sat., 20 mL)and extracted with DCM ( 3 X 10 mL). The combined organics were dried overanhydrous Na2SO4.The solvent was removed under vacuum. All the products were purified by silica gel column chromatography (hexane /EtOAc=6 / 1). 4.2.11 (2-Naphthyl)-methyl 4,6-di-O-acetyl-2,3-dideoxy-α-d-erythro-hex-2-enopyranoside (3k) White solid; mp=72 °C, [α]25D[α]D25 +42 (c 0.73 CHCl3, α only), {lit.:7e mp=72 °C, [α]23D[α]D23 +12 (c 1.0, CHCl3, α:β=9:1)};1H NMR (400 MHz, CDCl3): δ 2.10 (s, 3H), 2.11 (s, 3H), 4.17-4.29 (m, 3H), 4.78 (d, J=11.9 Hz, 1H), 4.99 (d, J=11.8 Hz, 1H), 5.20 (s, 1H), 5.36 (d, J=9.2 Hz, 1H), 5.88-5.95 (m, 2H), 7.49-7.51 (m, 3H), 7.83-7.86 (m, 4H) ppm; IR (film, cm-1): 3053, 2926, 2876, 1947, 1741, 1506, 1423, 1375, 1230, 1044, 963, 901, 860, 817, 742, 606, 535, 474; MS (ESI) m/z: 393.0 ([M+Na]+,100), 212.9 (25), 153.1 (60), 111.2 (20).
  • 20
  • [ 1592-38-7 ]
  • [ 66-99-9 ]
  • [ 93-09-4 ]
YieldReaction ConditionsOperation in experiment
1: 75% 2: 9% With tert-butyl 1-hydroxy-2-methyl-6-trifluoromethyl-1H-indole-3-carboxylate; oxygen; copper chloride (I) In N,N-dimethyl-formamide at 50℃; for 12h; 2.2 General procedure for aerobic oxidation of allylic and benzylic alcohols General procedure: To a 10 mL Schlenk tube, NHI-1 (0.2 mmol, 63 mg) and CuCl (0.2 mmol, 19.6 mg) and DMF (2 mL) were added and stirred at 50 °C for about 30 min to form a dark red solution. Alcohol 11 (2 mmol) was added, the mixture was left to stir at 50 °C under an oxygen balloon (1 atm). The reaction progress was monitored by TLC or GC. After completion, the mixture was allowed to cool to room temperature, quenched with 1M HCl and diluted with H2O (50 mL), extracted with EtOAc (EA) (10 mL × 3), the combined organic layer was washed with brine and dried over MgSO4, the crude was purified by flash column chromatography (EtOAc : hexane = 1 : 10 to 1: 3) to afford ketone or aldehyde 12.
1: 51% 2: 41% With 2.9-dimethyl-1,10-phenanthroline; oxygen; Sodium hydrogenocarbonate In lithium hydroxide monohydrate at 100℃; for 24h;
With oxygen; HNO3 In 1,4-dioxane; lithium hydroxide monohydrate at 90℃; for 5h; chemoselective reaction;
1: 13 %Chromat. 2: 41.9 %Chromat. With oxygen; palladium diacetate In neat (no solvent) at 150℃; for 15h;
1: 70 %Chromat. 2: 3 %Chromat. With sulfuric acid; dihydrogen peroxide; C23H30CuN2O3 In acetonitrile at 70℃; for 2h; 4.6 Catalytic oxidation of alcohols General procedure: A typical procedure using complex 3 as catalyst and H2O2 as oxidant is as follows. An alcohol substrate (1.0mmol), complex 3 (2.0mol%), H2SO4 (1.0mmol) and H2O2 (8.0mmol) were mixed in 2.0mL CH3CN. The solution was stirred at 70°C for 2h. The reaction yields were analyzed by GC.

  • 21
  • [ 1592-38-7 ]
  • [ 70-55-3 ]
  • [ 125640-81-5 ]
YieldReaction ConditionsOperation in experiment
96% With potassium hydroxide In toluene at 130℃; for 96h; Inert atmosphere;
91% With [(η5-C5Me5)Ir(6,6'-dihydroxy-2,2'-bipyridine)(H2O)]OTf2; caesium carbonate In water at 120℃; for 15h; Inert atmosphere; Schlenk technique;
91% With [(η5-C5Me5)Ir(6,6'-dihydroxy-2,2'-bipyridine)(H2O)]OTf2; caesium carbonate In water at 120℃; for 15h; Schlenk technique; 14 Example 14: 4-Methyl -N- (2- naphthylmethyl) benzenesulfonamide 4-methyl-benzenesulfonamide (171mg, 1mmol), catalyst A (8.3mg, 0.01mmol, 1mol%), cesium carbonate (33mg, 0.1mmol, 0.1equiv.), 2- naphthalene-methanol (190mg, 1.2mmol) and water (1ml) were successively added to the reaction flask 25mlSchlenk.After the reaction mixture was reacted at 120 15 hours, cooled to room temperature.A large amount of precipitated, water was removed by filtration, the filter cake was washed with water three times to give the title compound, yield: 91%
91% With C20H26ClIrN3O(1+)*F6P(1-); sodium carbonate In water at 110℃; for 24h; Inert atmosphere; Schlenk technique; Glovebox;
87% With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; potassium <i>tert</i>-butylate In toluene for 17h; Inert atmosphere; Reflux;
80% With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; potassium carbonate; bis[2-(diphenylphosphino)phenyl] ether In 5,5-dimethyl-1,3-cyclohexadiene at 20 - 150℃; for 24.1667h; Inert atmosphere;
75% With tris(pentafluorophenyl)borate In chlorobenzene at 110℃; for 48h; Molecular sieve; Schlenk technique; Inert atmosphere; Sealed tube; chemoselective reaction;
45% In nitromethane at 100℃; for 8h;

  • 22
  • [ 532-02-5 ]
  • [ 1592-38-7 ]
  • 23
  • [ 1592-38-7 ]
  • [ 21969-45-9 ]
YieldReaction ConditionsOperation in experiment
62% With Dimethyl oxalate; manganese; 1,2-bis(diphenylphosphino)ethane nickel(II) chloride; lithium bromide In N,N-dimethyl-formamide at 110℃; for 16h; Inert atmosphere; Sealed tube; Synthesis of 2a; Typical Procedure General procedure: The procedure was conducted in an argon-filled glove box. A reaction tube equipped with a magnetic stir bar was charged with Ni(dppe)Cl2(10.6 mg, 0.02 mmol), Mn (44.0 mg, 0.8 mmol), alcohol 1a (48.8 mg,0.4 mmol), DMO (94.5 mg, 0.8 mmol), LiBr (34.7 mg, 0.4 mmol), and DMF (1.5 mL). The reaction tube was then sealed and removed from the glove box. The reaction mixture was stirred at 110 °C for 16 h. After cooling to r.t., the mixture was diluted with EtOAc (40 mL) and washed with water, brine, dried over anhydrous Na2SO4, and concentrated in vacuum. The residue was purified by flash chromatography on silica gel to afford the desired product 2a.
Multi-step reaction with 2 steps 1: Py 2: dioxane / Irradiation
Multi-step reaction with 2 steps 1: dmap / dichloromethane / 24 °C / Inert atmosphere 2: zinc; 1,1'-bis-(diphenylphosphino)ferrocene; [1,1'-bis(diphenylphosphino)ferrocene]nickel(II) chloride / N,N-dimethyl acetamide / 20 h / 24 °C / Glovebox; Inert atmosphere
Multi-step reaction with 2 steps 1: dmap / dichloromethane / 24 °C / Inert atmosphere 2: nickel(II) bromide dimethoxyethane; zinc; bathophenanthroline; 4-tolyl iodide / N,N-dimethyl acetamide / 20 h / 24 °C / Glovebox; Inert atmosphere

  • 24
  • [ 6945-67-1 ]
  • 2-[1-hydroxy-1-[4-(naphth-2-ylmethoxy)pyrid-2-yl]propyl]thiazole [ No CAS ]
  • [ 1592-38-7 ]
  • 2-bromo-4-(naphth-2-ylmethoxy)pyridine [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% The 2-[1-hydroxy-1-[4-(naphth-2-ylmethoxy)pyrid-2-yl]propyl]thiazole used as a starting material was obtained as follows: 2-Naphthylmethanol was reacted with <strong>[6945-67-1]2-bromo-4-nitropyridine</strong> (Chem. Abstracts, 1951, 45, 9536) using the conditions described in the first paragraph of the portion of Example 4 which is concerned with the preparation of starting materials except that the reaction mixture was stirred at ambient temperature for 2 hours. There was thus obtained 2-bromo-4-(naphth-2-ylmethoxy)pyridine in 80% yield, m.p. 99-100 C.
  • 25
  • 2-[1-hydroxy-1-[6-(naphth-2-ylmethoxy)pyrimidin-4-yl]propyl]thiazole [ No CAS ]
  • [ 1592-38-7 ]
  • [ 19646-06-1 ]
  • 6-iodo-4-(naphth-2-ylmethoxy)pyrimidine [ No CAS ]
YieldReaction ConditionsOperation in experiment
39% Notes The 2-[1-hydroxy-1-[6-(naphth-2-ylmethoxy)pyrimidin-4-yl]propyl]thiazole used as a starting material was obtained as follows: 2-Naphthylmethanol was reacted with 4,6-diiodopyrimidine (J. Med. Pharm. Chem. 1962, 1335) using the conditions described in the first paragraph of the portion of Example 4 which is concerned with the preparation of starting materials except that the reaction mixture was stirred at ambient temperature for 2 hours. There was thus obtained 6-iodo-4-(naphth-2-ylmethoxy)pyrimidine as an oil in 39% yield.
  • 26
  • [ 130723-13-6 ]
  • (2RS,4SR)-4-hydroxy-2-methyl-4-[3-(naphth-2-ylmethoxy)-5-trifluoromethylphenyl]tetrahydropyran [ No CAS ]
  • [ 1592-38-7 ]
  • 3-(naphth-2-ylmethoxy)-5-trifluoromethylbromobenzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% The (2RS,4SR)-4-hydroxy-2-methyl-4-[3-(naphth-2-ylmethoxy)-5-trifluoromethylphenyl]tetrahydropyran used as a starting material was obtained as follows: Using the procedure described in the first paragraph of Note e. below Table IV in Example 15, 2-naphthalenemethanol was reacted with <strong>[130723-13-6]3-fluoro-5-trifluoromethylbromobenzene</strong> to give 3-(naphth-2-ylmethoxy)-5-trifluoromethylbromobenzene (80%), m.p. 68-70 C.
  • 27
  • [ 5054-59-1 ]
  • [ 1592-38-7 ]
  • [ 1061604-62-3 ]
YieldReaction ConditionsOperation in experiment
30% With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 0 - 20℃; Example 14 2-(2,6-Dioxo-piperidin-3-yl)-4-(naphthalene-2-yImethoxy)-isoindole-l,3-dione[202] A mixture of triphenylphosphine ( 1.15 g, 4.40 mmol) and 2- naphthalenemethanol (0.58 g, 3.6 mmol) was stirred in THF (10 mL) at 0 0C. Keeping the reaction mixture at 0 0C, a solution of diisopropylazodicarboxylate (0.87 mL, 4.4 mmol) in THF (2.1 mL) was added dropwise. 2-(2,6-Dioxo-piperidin-3-yl)-4-hydroxy-isoindole-l,3- dione (1.00 g, 3.60 mmol) was then added as a solid, the reaction mixture was stirred at 0 C for 1 h and then at room temperature overnight. The precipitate was filtered, washed with additional THF (10 mL) and dried. The resulting solid was stirred in hexane (50 mL) for 2 <n="66"/>h, filtered and dried. The resulting solid was heated to reflux in methanol (50 mL) for 1 h, filtered and dried to afford the product as a white solid (0.46 g, 30% yield); mp > 260 0C; HPLC, Waters Symmetry C- 18, 3.9 x 150 mm, 5 mum, 1 mL/min, 240 nm, 50/50 CH3CN/0.1 % H3PO4, 6.20 (99.48%); 1H NMR (DMSO-J6) delta 2.02-2.07 (m, IH), 2.44-2.62 (m, 2H), 2.82-2.97 (m, IH), 5.12 (dd, J = 12.5 Hz, J = 5.3 Hz, IH), 5.54 (s, 2H), 7.46-8.05 (m, 10H), 11.13 (s, IH); 13C NMR (DMSO-J6) delta 22.0, 31.0, 48.8, 70.3, 115.6, 116.7, 120.4, 125.3, 126.1, 126.3, 126.4, 127.7, 127.8, 128.2, 132.6, 132.7, 133.3, 133.8, 137.0, 155.6, 165.4, 166.8, 169.9, 172.8; Anal. Calcd for C24Hi8N2O5: C, 69.39; H, 4.02; N, 6.61. Found: C, 69.56; H, 4.38; N, 6.76.
  • 28
  • [ 1592-38-7 ]
  • [ 75-16-1 ]
  • [ 939-27-5 ]
YieldReaction ConditionsOperation in experiment
4% In diethyl ether; toluene at 25℃; for 15h;
  • 29
  • [ 1592-38-7 ]
  • [ 75-36-5 ]
  • [ 35480-23-0 ]
YieldReaction ConditionsOperation in experiment
95% With triethylamine In dichloromethane at 0 - 20℃;
83% With triethylamine In dichloromethane at 20℃; 3. General procedure for preparation of (hetero)benzyl acetates 5a-5l and 5q-5s General procedure: To a solution of benzyl or hetero-benzyl alcohols (2.0 mmol) in CH2Cl2 (6 mL) was added acetyl chloride (173 mg, 2.2 mmol) and Et3N (202 mg, 2.0 mmol). The reaction mixture was stirred at room temperature until completion (monitored by TLC), and then water (30 mL) was added. The aqueous layer was extracted with CH2Cl2 (3 × 5 mL). The combined organic layers were washed with brine, dried over anhydrous Na2SO4, filtered, and concentrated in vacuo. The residue was puried by flash chromatography (petroleum ether/ethyl acetate 300:1 to 50:1) to give the products 5a-5l and 5q-5t.
77% In dichloromethane at 20℃;
  • 30
  • [ 1592-38-7 ]
  • [ 74-88-4 ]
  • [ 42101-92-8 ]
YieldReaction ConditionsOperation in experiment
99% Stage #1: 2-Naphthalenemethanol With sodium hydride In tetrahydrofuran; paraffin oil at 45℃; for 1h; Inert atmosphere; Stage #2: methyl iodide In tetrahydrofuran; paraffin oil at 45℃; Inert atmosphere;
95% With sodium hydride In mineral oil at 0 - 20℃; Inert atmosphere;
65% With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 15h;
With sodium hydride In tetrahydrofuran at 20 - 60℃;
Stage #1: 2-Naphthalenemethanol With sodium hydride In tetrahydrofuran at 0℃; for 1h; Inert atmosphere; Stage #2: methyl iodide In tetrahydrofuran at 0 - 20℃; Inert atmosphere;
0.79 g Stage #1: 2-Naphthalenemethanol With sodium hydride In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: methyl iodide In tetrahydrofuran at 20℃; Inert atmosphere; General Procedure B: General procedure: To a solution of the NaH (2.4 equiv) in THF (0.5 M) was added a solutionof the alcohol (1.0 equiv) in THF (1.0 M). The reaction mixture was stirred at room temperaturefor 1 hour and MeI (2.3 equiv) was then added. The reaction mixture was stirred until thereaction was judged to have reached completion by TLC. After addition of water to the reactionmixture, the layers were separated and the aqueous phase was extracted with EtOAC (3x). Thecombined organic layers were washed with brine (1x) and dried over MgSO4 and concentratedunder reduced pressure. The crude residue was then purified by flash column chromatography onsilica gel (hexanes/EtOAc) to yield the pure ether.

  • 31
  • [ 1592-38-7 ]
  • [ 84956-71-8 ]
  • 2-tert-butyl-4-chloro-5-(2-naphthylmethyl)oxy-3-(2H)-pyridazinone [ No CAS ]
  • 32
  • [ 592-35-8 ]
  • [ 1592-38-7 ]
  • [ 1158827-16-7 ]
  • 33
  • [ 110-87-2 ]
  • [ 1592-38-7 ]
  • [ 1205051-21-3 ]
YieldReaction ConditionsOperation in experiment
96% With pyridinium 4-toluenesulfonate In dichloromethane Reflux;
92% With BINOL H; diphenyldisulfane In dichloromethane at 20℃; for 6h; Schlenk technique; Irradiation; Inert atmosphere; 3. General Procedure for BINOL-Catalyzed Acetalization underVisible Light General procedure: To an oven-dried round-bottom Schlenk tube (10 mL) with a magnetic stir bar, 3,4-dihydro-2H-pyran (0.101 g, 0.6 mmol, 1.2 eq) and 3-phenyl-1-propanol(0.068 g, 0.5mmol, 1.0 equiv.), BINOL H (3.10 mg, 10 μmol, 0.01 equiv.), PhSSPh (2.20 mg, 10 μmol,0.02 equiv.) and dry dichloromethane (0.50 mL) were added and the mixture wasallowed to irradiate under purple LEDs reactor (6 W,λmax 400 nm)(followed by TLC).The pure products were purified by column chromatography (SiO2, hexane: ethylacetate=15 :1).
  • 34
  • [ 1592-38-7 ]
  • [ 91-57-6 ]
YieldReaction ConditionsOperation in experiment
73% With palladium 10% on activated carbon; hydrogen; In ethanol; at 100℃; under 760.051 - 1520.1 Torr; for 24h; General procedure: A: A mixture of ketone or aldehyde 1 (0.50 mmol), Pd/C (10.0 mg, 10 wt% palladium on activated carbon paste and 50% moisture, 0.9 mol% [Pd] based on starting material 1) in ethanol/water (30/1, 3 mL) was added into a Schlenk flask (25 mL) and stirred at room temperature. Then N2H4·H2O (100 mg, 2.0 mmol, 4.0 equiv) was added and the mixture was stirred at 100 C. After the reaction was finished, the solvent was evaporated under reduced pressure and the residue was purified by column chromatography (petroleum ether/ethyl acetate 50:1 to 20:1) to provide hydrocarbons 2. B: A mixture of ketone or aldehyde 1 (0.50 mmol), Pd/C (10.0 mg, 10 wt% palladium on activated carbon paste and 50% moisture, 0.9 mol% [Pd] based on starting material 1) in ethanol (3 mL) was added into a Schlenk flask (25 mL) and stirred at room temperature. The reaction system was replaced 3 times with nitrogen and filled with hydrogen at 1 atmospheric pressure. Then the mixture was stirred at 100 C. After the reaction was finished and released of the hydrogen, the solvent was evaporated under reduced pressure and the residue was purified by column chromatography (petroleum ether/ethyl acetate 50:1 to 20:1) to provide hydrocarbons 2. C: A mixture of ketone or aldehyde 1 (0.50 mmol), Pd/C (10.0 mg, 10 wt% palladium on activated carbon paste and 50% moisture, 0.9 mol% [Pd] based on starting material 1) in ethanol (3 mL) was added into a Schlenk flask (25 mL) and stirred at room temperature. Then ammonium formate (126 mg, 2.0 mmol, 4.0 equiv) was added and the mixture was stirred at 100 C. After the reaction was finished, the solvent was evaporated under reduced pressure and the residue was purified by column chromatography (petroleum ether/ethyl acetate 50:1 to 20:1) to provide hydrocarbons 2.
  • 35
  • [ 5683-31-8 ]
  • [ 1592-38-7 ]
  • [ 1234580-88-1 ]
  • 36
  • [ 1592-38-7 ]
  • [ 92420-89-8 ]
  • [ 1198406-07-3 ]
  • 37
  • [ 1592-38-7 ]
  • [ 4029-41-8 ]
  • [ 1226502-13-1 ]
YieldReaction ConditionsOperation in experiment
83% With sodium hydride; In tetrahydrofuran; mineral oil; at 0 - 20℃; for 2.0h;Inert atmosphere; EXAMPLE 8N-{3-[(2-naphthyl)methoxy]quinoxalin-2-yl}-4-toluene-sulfonamide (Compound 13); <strong>[4029-41-8]N-(3-Chloroquinoxalin-2-yl)-4-toluenesulfonamide</strong> (Compound AB) (70.0 mg, 0.210 mmol) and 2-naphthaleneethanol (40.0 mg, 252 mmol) were dissolved in tetrahydrofuran (1.5 mL). To this, 60% sodium hydride (in oil) (18.5 mg, 0.462 mmol) was added under a nitrogen atmosphere at 0 C. and the mixture was stirred at room temperature for 2 hours. Then, a saturated aqueous ammonium chloride solution was added to the reaction mixture, and extraction with ethyl acetate was performed, followed by washing with brine and drying over anhydrous sodium sulfate. The solvent was evaporated off under reduced pressure, and the residue was subjected to slurry purification using methanol, to give N-{3-[(2-naphthyl)methoxy]quinoxalin-2-yl}-4-toluene-sulfonamide (Compound 13) (79.0 mg, yield: 83%).ESIMS m/z: 446 (M+H)+; 1H-NMR (300 MHz, DMSO-d6, delta): 2.34 (s, 3H), 5.70 (s, 2H), 7.40 (d, J=8.1 Hz, 2H), 7.53-7.56 (m, 4H), 7.71-8.12 (m, 9H), 11.33 (br s, 1H).
  • 38
  • [ 1592-38-7 ]
  • [ 4760-34-3 ]
  • [ 3367-02-0 ]
YieldReaction ConditionsOperation in experiment
93% With dimethyl sulfoxide; 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide In ethyl acetate at 0 - 25℃; for 3h; Inert atmosphere; chemoselective reaction; General procedure for the one-pot synthesis of benzimidazoles and benzothiazoles: General procedure: to a solution of alcohol (1.1 mmol) in a mixture of solvents ethyl acetate (4 mL) and DMSO (2 mL), was added T3P (2 mmol, 50% solution in ethyl acetate) at 0 °C and the resulting reaction mixture was stirred at room temperature for 1-2 h under nitrogen atmosphere. The reaction was monitored by TLC, 1,2-phenylenediamine (1 mmol) was added and stirred further for 1-2 h. After completion of the reaction, the mixture was diluted with water (20 mL) and neutralized with 10% NaHCO3 solution. The product was extracted with ethyl acetate (10 mL) and the combined organic phase was washed with water (10 mL) and brine solution. The organic phase was dried over anhydrous Na2SO4. The solvent was dried under reduced pressure to afford a crude product, which was purified on silica gel using ethyl acetate and petroleum ether. For the conversion of alcohols to benzothiazoles the same procedure as above was followed except the use of o-aminothiophenol, instead of 1,2-phenylenediamine.
  • 39
  • [ 1592-38-7 ]
  • [ 13323-81-4 ]
  • [ 56345-34-7 ]
YieldReaction ConditionsOperation in experiment
85% With cis-tetracarbonyl(1,1'-methylene-3,3'-dimethyl-4,4'-diimidazoline-2,2'-diylidene)molybdenum(0); sodium hydroxide In toluene at 140℃; for 6h; Inert atmosphere; Sealed tube;
68.9% With trans,cis-[RuCl2(2-(aminomethyl)pyridine)(triphenylphosphane)2]; potassium <i>tert</i>-butylate In toluene at 105℃; for 22h; Inert atmosphere; Schlenk technique; 4.2. General procedure for RuCl2(PPh3)2(2-NH2CH2Py) catalyzedb-alkylation reactions of secondary alcohols with primary alcohols General procedure: A mixture of RuCl2(PPh3)2(2-NH2CH2Py) (1 mol%), KOtBu(1 equiv.), a secondary alcohol (1 equiv) and a primary alcohol(2 equiv.) in 1 mL of toluene or dioxane was heated for a period of time. The product was extracted with diethyl ether, purified bycolumn chromatography on silica gel using petroleum ether/diethyl ether 6:1 and 4:1 as the eluents, and identified by NMR.
87 %Spectr. With 1,3-bis-(diphenylphosphino)propane; copper(I) bromide; sodium hydroxide In para-xylene at 135℃; for 48h; Inert atmosphere;
With C51H41N3O2P2RuS; potassium <i>tert</i>-butylate In toluene at 110℃; for 1h; Schlenk technique; Inert atmosphere;
With [{MeO-C5H3N-C5H3N-CH(O)-C6H4-PPh2}Ru(CO)(PPh3)]Cl; potassium <i>tert</i>-butylate In toluene for 1.5h; Inert atmosphere; Schlenk technique; Reflux;
256.9 mg With Cp*IrCl[κ2(N,C)-{NH2C-(C6H5)2-2-C6H4}]; potassium <i>tert</i>-butylate; pentan-3-one In tert-Amyl alcohol at 23℃; for 24h; Inert atmosphere;
80 %Spectr. With C30H43ClCoN2P3(1+)*Cl(1-); sodium t-butanolate In toluene at 110℃; for 24h; Inert atmosphere; Glovebox; Sealed tube;

  • 40
  • [ 1592-38-7 ]
  • [ 62-53-3 ]
  • [ 181825-27-4 ]
YieldReaction ConditionsOperation in experiment
96% With [2-(4,5-dihydro-1H-imidazol-2-yl)-6-methoxypyridine](pentamethylcyclopentadienyl)chloride iridium(III); potassium hydroxide In water at 80℃; Schlenk technique; Inert atmosphere; 17 Example 17 Preparation of N-(2-naphthylmethyl)aniline from 2-naphthyl alcohol and aniline In a 10mL Schlenk tube, add 2-naphthalenemethanol (1.1mmol), aniline (1.0mmol), KOH (1.1mmol), H 2 O (2.0mL) and chloride monochloride·[2-(4,5-di Hydrogen-1H-imidazol-2-yl)-6-methoxypyridine]·(pentamethylcyclopentadienyl)iridium(III) (0.1 mol%). Under the protection of nitrogen, heat to 80°C for reaction. After completion, it was extracted with ethyl acetate (3×5.0 mL), the organic layers were combined, dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure to obtain a crude product. The crude product was purified with a mixture of ethyl acetate/petroleum ether (1/20) as the eluent and purified by silica gel chromatography to obtain a pure product with a yield of 96%.
95% With C36H35IrN2P(1+)*C32H12BF24(1-); potassium <i>tert</i>-butylate In diethylene glycol dimethyl ether at 50℃; for 24h; Inert atmosphere;
94% With [(η5-pentamethylcyclopentadienyl)IrIIIbis-(κC-1,3-dimethylimidazol-2-ylidene)Cl]BF4; potassium <i>tert</i>-butylate In toluene at 80℃; for 12h; 4.2. General method for the N-alkylation of amines with alcohols General procedure: To a 15 mL reaction tube in a glovebox, was added complex Ir3(0.5 mol%), KOtBu (75 mol%), the alcohol (0.5 mmol) and the amine(0.5 mmol) at room temperature. Then the tube was closed andremoved from the glovebox. The reaction mixture was stirred at 80 °C for 12 h. After cooling to room temperature, the reaction mixturewas diluted with ethyl acetate, filtered and dried under vacuum.The product was purified by column chromatography oversilica-gel (300-400 mesh) with an appropriate mixture of petroleum ether and ethyl acetate (80:1).
93% With potassium hydroxide In toluene at 110℃; for 24h; Inert atmosphere; Sealed tube; 10 Example 10: Hydrogen Transfer Reaction of 2-Naphthalenemethanol with Aniline Catalyzed by Carbon-Supported Rhodium Nanomaterials 2-Naphthylmethanol (1.3 mmol), carbon-supported Nd nanomaterial (20 mg), and potassium hydroxide (20 mg) were added to a reaction tube equipped with a magnetic stirrer 25 ml with a branch.The nitrogen gas was repeatedly pumped three times, and aniline (1 mmol) and toluene (3 ml) were successively added via a syringe and then sealed and reacted at 110°C for 24 hours.After the reaction is completed, the catalyst is removed by filtration, and the filtrate is extracted by adding water and ethyl acetate, and the organic phases are combined.After drying, filtration, concentration under reduced pressure, and silica gel column chromatography, N-(2-naphthyl)aniline was obtained (yield 93%).
92% With potassium hydroxide In toluene at 110℃; for 24h; Inert atmosphere;
92% With 1,10-Phenanthroline; tungsten hexacarbonyl; potassium <i>tert</i>-butylate In 1,4-dioxane at 130℃; for 24h;
86% With C20H26ClIrN3O(1+)*F6P(1-) In water at 110℃; for 24h; Inert atmosphere; Schlenk technique; Glovebox;
85% With C13H16MnN2O3S(1+)*Br(1-); potassium <i>tert</i>-butylate In toluene at 140℃; for 24h; Inert atmosphere;
85% With cis-tetracarbonyl(1,1'-methylene-3,3'-dimethyl-4,4'-diimidazoline-2,2'-diylidene)molybdenum(0); potassium <i>tert</i>-butylate In hexane at 130℃; for 24h; Sealed tube;
84% With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; 2-(2-(diphenylphosphanyl)phenyl)benzo[d]oxazole; potassium hydroxide In toluene at 110℃; for 24h; Schlenk technique; Inert atmosphere; 4.3. General procedure for alkylation reactions General procedure: [Cp*IrCl2]2 (1 mol %, 0.01 mmol, 8.0 mg), 4a (2 mol %, 0.02 mmol,7.6 mg), KOH (10 mol %, 0.1 mmol, 5.6 mg), and toluene (5 mL) wereadded to a 25mL Schlenk tube with stirring under N2 at roomtemperature. Then ketones/secondary alcohols/amines (1 mmol),primary alcohols (1.1 mmol) were added by syringe. The reactionmixture was heated to 110 °C under reflux in an oil bath for 24 h. Itwas cooled to ambient temperature. Then it was concentrated invacuo, and purified by flash column chromatography with petroleumether/ethyl acetate to afford the corresponding alkylatedproduct.
84% With C34H38Cl4N6Ni2; potassium 2-methylbutan-2-olate In toluene at 140℃; for 12h; Inert atmosphere; 2. General procedure for Ni-catalyzed N-alkylation of aromatic amines with alcohols General procedure: To a Young tube, was charged with Ni4 (39 mg, 0.05 mmol), t-AmOK (191 mg, 1.5 mmol) and toluene (4 mL). Stirred the mixture for 2-3 minutes. Then, aromatic amine (1.0 mmol) and alcohol (2.0 mmol) were added. After stirring the resultant mixture at 140 oC for 12 h, the reaction temperature was allowed to cool to room temperature. Solvent was removed in vacuo and the desired product was isolated by column chromatography.
80% With potassium <i>tert</i>-butylate; C38H37ClN2PRu(1+)*C32H12BF24(1-) In neat (no solvent) at 70℃; for 12h; Sealed tube; Inert atmosphere; Schlenk technique; Green chemistry;
80% With potassium <i>tert</i>-butylate In octane at 140℃; for 24h; Inert atmosphere; Sealed tube;
87 %Spectr. With C27H19ClNO3PRu; potassium <i>tert</i>-butylate at 110 - 150℃; for 4h; Inert atmosphere;

Reference: [1]Current Patent Assignee: UNIV GANNAN MEDICAL - CN111848412, 2020, A Location in patent: Paragraph 0185-0191
[2]Li, Jia-Qi; Andersson, Pher G. [Chemical Communications, 2013, vol. 49, # 55, p. 6131 - 6133]
[3]Feng, Xinshu; Huang, Ming [Polyhedron, 2021, vol. 205]
[4]Current Patent Assignee: SOOCHOW UNIVERSITY (SUZHOU) - CN107954879, 2018, A Location in patent: Paragraph 0052
[5]Guo, Bin; Li, Hong-Xi; Zhang, Shi-Qi; Young, David James; Lang, Jian-Ping [ChemCatChem, 2018, vol. 10, # 24, p. 5627 - 5636]
[6]Lan, Xiao-Bing; Ye, Zongren; Yang, Chenhui; Li, Weikang; Liu, Jiahao; Huang, Ming; Liu, Yan; Ke, Zhuofeng [ChemSusChem, 2021, vol. 14, # 3, p. 860 - 865]
[7]Huang, Ming; Li, Yinwu; Liu, Jiahao; Lan, Xiao-Bing; Liu, Yan; Zhao, Cunyuan; Ke, Zhuofeng [Green Chemistry, 2019, vol. 21, # 2, p. 219 - 224]
[8]Das, Kalicharan; Mondal, Avijit; Pal, Debjyoti; Srivastava, Hemant Kumar; Srimani, Dipankar [Organometallics, 2019, vol. 38, # 8, p. 1815 - 1825]
[9]Huang, Ming; Huang, Yong-Liang; Ke, Zhuofeng; Lan, Xiao-Bing; Li, Weikang; Liu, Jiahao; Liu, Yan; Ye, Zongren; Zhao, Cunyuan [ACS Catalysis, 2021, vol. 11, p. 10377 - 10382]
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[14]Location in patent: experimental part Lee, Chun-Chin; Chu, Wan-Yi; Liu, Yi-Hong; Peng, Shie-Ming; Liu, Shiuh-Tzung [European Journal of Inorganic Chemistry, 2011, # 31, p. 4801 - 4806]
  • 42
  • [ 67-56-1 ]
  • [ 1592-38-7 ]
  • [ 2459-25-8 ]
YieldReaction ConditionsOperation in experiment
98% With oxygen; potassium carbonate at 60℃; for 20h;
93% With bismuth(III) chloride; palladium diacetate; potassium carbonate at 20℃; for 2h; chemoselective reaction;
93% With carbon tetrabromide; oxygen at 20℃; for 20h; Irradiation; General procedure: Typical procedure: A solution of 4-tert-butylbenzyl alcohol (1a, 0.3 mmol) and CBr4 (0.09 mmol) in dry MeOH (4 mL) in a pyrex test tube, purged with an O2-balloon, was stirred and irradiated externally with four 22 W fluorescent lamps for 20 h. The reaction mixture was concentrated in vacuo. Purification of the crude product by PTLC (toluene) provided methyl 4-tert-butylbenzoate (2a) (Rf = 0.40, 54.0 mg, 94%).
90% With oxygen at 70℃; for 16h;
89% With trichloro(2,2':6',2''-terpyridine)rhodium(III); sodium hydrogencarbonate at 90℃; for 48h; Green chemistry; chemoselective reaction;
85% With Pyridine-2,6-dicarboxylic acid; dihydrogen peroxide; trifluoroacetic acid; zinc dibromide In water at 20℃; for 16h;
84% With dibromamine-T; potassium carbonate In acetonitrile at 20℃; for 1h; General procedure for the synthesis of methyl ester General procedure: To a solution of alcohol(1 mmol) in a mixture of MeCN and MeOH (5:1, 2.4 mL) was added TsNBr2(2.5 mmol) and K2CO3 (5 mmol) and stirred at room temperature. Aftercompletion of the reaction (TLC) sodium thiosulfate was added and thereaction mixture was stirred for 10 min. The reaction mixture was extracted indiethyl ether and hexane (1:1), dried, (Na2SO4) and concentrated. Purificationof the crude product by flash chromatography on silica gel (230-400 mesh)with petroleum ether-EtOAc as eluent gave the pure product
82% With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; (2-((2-(diphenylphosphanyl)ethyl)(quinolin-2-ylmethyl)amino)ethyl)diphenylphosphine oxide; potassium carbonate In n-heptane at 120℃; for 16h;
82% With potassium carbonate at 55℃; for 24h; S6. Procedure for the synthesis of esters General procedure: A magnetic stir bar and the alcohol substrate were transferred to 20 mL glass tube and then 2 mL of MeOH oralcohol was added. Then, 35 mg catalyst and 10 mol% of K2CO3 were added. The glass tube containingreaction mixture was fitted with septum and connected to a balloon containing one bar air. Then the glass tubewas placed into a preheated aluminum block at 60°C. Temperature inside the reaction tube was measured tobe 55 oC and this temperature has been taken as the reaction temperature. After completion of the reaction,the glass tube was cooled down to room temperature. Af terwards, the catalyst was f iltered-off and washedwith methanol. The solvent from the filtrate containing the reaction products was removed in vacuum and thecorresponding ester was purified by column chromatography. Products were analyzed by GC-MS and NMRspectroscopy analysis. In the case of yields determined the by GC, 100 μL n-hexadecane was added to thereaction vial containing the products and diluted with ethyl acetate. Then catalyst was f iltered through a plugof silica and the filtrate containing product was analyzed by GC.
72% With potassium chloride; dihydrogen peroxide; C5H12CrMo6O25(3-)*3C16H36N(1+) In water at 65℃; for 36h; Schlenk technique;
95 %Chromat. With oxygen; potassium carbonate at 60℃; for 24h; Schlenk technique; Green chemistry;
With bismuth(lll) trifluoromethanesulfonate; dichloro bis(acetonitrile) palladium(II); oxygen; potassium carbonate at 60℃; for 3h; Schlenk technique; 3.20 4.2.1 General procedure for the synthesis of 2 in Table2 General procedure: To a 25-mL Schlenk tube equipped with a magnetic stirrer, PdCl2(CH3CN)2 (0.05mol, 5mol%), Bi(OTf)3 (0.05mol, 5mol%), K2CO3 (1mmol) were added. Substrates 1 (1mmol) and MeOH (2mL) were added subsequently. The reaction tube was vacuumed and backfilled with oxygen (3 times). Then the reaction mixture was stirred at 60°C for 3h in the presence of an oxygen balloon. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate. Subsequently, the combined organic layer was concentrated under reduced pressure and the crude product was purified by column chromatography with hexane/ethyl acetate to afford the corresponding products 2.

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[5]Cheng, Junjie; Zhu, Meijuan; Wang, Chao; Li, Junjun; Jiang, Xue; Wei, Yawen; Tang, Weijun; Xue, Dong; Xiao, Jianliang [Chemical Science, 2016, vol. 7, # 7, p. 4428 - 4434]
[6]Location in patent: experimental part Wu, Xiao-Feng [Chemistry - A European Journal, 2012, vol. 18, # 29, p. 8912 - 8915]
[7]Rajbongshi, Kamal Krishna; Sarma, Manas Jyoti; Phukan, Prodeep [Tetrahedron Letters, 2014, vol. 55, # 39, p. 5358 - 5360]
[8]Jiang, Xiaolin; Zhang, Jiahui; Zhao, Dongmei; Li, Yuehui [Chemical Communications, 2019, vol. 55, # 19, p. 2797 - 2800]
[9]Bartling, Stephan; Beller, Matthias; Chandrashekhar, Vishwas G.; Jagadeesh, Rajenahally V.; Rabeah, Jabor; Rockstroh, Nils; Senthamarai, Thirusangumurugan [Chem, 2022, vol. 8, # 2, p. 508 - 531]
[10]Wang, Jingjing; Jiang, Feng; Tao, Chaofu; Yu, Han; Ruhlmann, Laurent; Wei, Yongge [Green Chemistry, 2021, vol. 23, # 7, p. 2652 - 2657]
[11]Jagadeesh, Rajenahally V.; Junge, Henrik; Pohl, Marga-Martina; Radnik, Joerg; Brueckner, Angelika; Beller, Matthias [Journal of the American Chemical Society, 2013, vol. 135, # 29, p. 10776 - 10782]
[12]Hu, Yongke; Li, Bindong [Tetrahedron, 2017, vol. 73, # 52, p. 7301 - 7307]
  • 43
  • [ 1395348-84-1 ]
  • [ 1592-38-7 ]
YieldReaction ConditionsOperation in experiment
89% With 1,11-bis(3-methyl-3H-imidazolium-1-yl)-3,6,9-trioxaundecane di(methanesulfonate) In methanol at 20℃; for 1.33333h; General procedure for deprotection of TBDMS ether using [tetraEG(mim)2][OMs]2 General procedure: A mixture of TBDMS ether (1.0 mmol) and [tetraEG(mim)2][OMs]2 IL (0.2 mmol) in methanol (4 mL) was stirred at room temperature up to the completion of reaction. Reaction progress was monitored by thin layer chromatography (TLC). After completion of the reaction, methanol was removed under reduced pressure and the residue was extracted with diethyl ether and dried over sodium sulfate. The diethyl ether was evaporated under reduced pressure to afford respective products.
  • 44
  • [ 1592-38-7 ]
  • [ 75-16-1 ]
  • [ 939-27-5 ]
  • [ 91-57-6 ]
YieldReaction ConditionsOperation in experiment
1: 72% 2: 8% With bis(1,5-cyclooctadiene)nickel (0); 2-[2-(dicyclohexylphosphino)-phenyl]-1-methyl-1H-indole In toluene at 80℃; for 12h; Schlenk technique; Sealed tube;
1: 68% 2: 9% With bis(acetylacetonate)nickel(II); 1,1'-bis(dicyclohexylphosphinocyclopentadienyl)iron In toluene at 60℃; for 24h; Inert atmosphere;
  • 45
  • [ 120-72-9 ]
  • [ 1592-38-7 ]
  • 3,3′-(naphthalen-2-ylmethylene)bis(1H-indole) [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With copper(II) ferrite; lithium tert-butoxide In neat (no solvent) at 80℃; for 24h; 2.1. General procedure 1 for the synthesis of compounds 1-11, 16-20 General procedure: A mixture of Indole (0.3 mmol), Alcohol (1.2 mmol), CuFe2O4 (7.2mg, 10 mol%) and LiOtBu (24 mg, 1 equiv.) were charged in a pressuretube. The pressure tube was immersed in a pre-heated oil bath at 80 Cand stirred for 24 h. After cooling, the reaction mixture was filtered overa plug of Celite with hot water to eliminate the excess of alcohol. Theorganic phase was washed by Ethyl acetate, then dried by sodium sulfate(Na2SO4). The concentrated residue was purified by column chromatography(Hexane/Ethyl acetate).
80% Stage #1: 2-Naphthalenemethanol With iodine; oxygen In ethyl acetate for 20h; Irradiation; Stage #2: indole In ethyl acetate at 20℃; for 0.166667h;
63% With sodium hydride; 3,4-dihydronaphthalene-1(2H)-one In 5,5-dimethyl-1,3-cyclohexadiene at 150℃; for 6h; Schlenk technique; Inert atmosphere; Sealed tube; Synthesis of 3; General Procedure General procedure: To a 25 mL flame-dried Schlenk tube containing a stirring bar wasadded indole (0.4 mmol, 46.8 mg.), NaOEt (0.8 mmol, 54.4 mg), toluene(0.5 mL) and 1-tetralone (0.4 mmol, 58.4 mg), sequentially undernitrogen. The tube was sealed and stirred at 150 °C for 6 h. Upon completion,the reaction mixture was diluted with EtOAc (5.0 mL) and filteredthrough a short pad of silica gel washing with EtOAc (20 mL).The filtrate was concentrated and purified by silica gel column chromatographyto provide the product.
  • 46
  • [ 1592-38-7 ]
  • [ 4049-33-6 ]
  • C22H24O8 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With boron trifluoride diethyl etherate; In dichloromethane; at 0 - 20℃; General procedure: Peracetylated xylose 6 (319 mg, 1.00 mmol) and 2-naphthalenemethanol (273 mg, 1.50 mmol) were dissolved in CH2Cl2 (3 mL) and BF3·Et2O (190 μL, 1.50 mmol) was added dropwise to the solution at 0 C. The mixture was allowed to reach rt and stirred for 1.5 h. CH2Cl2 was added and the mixture was washed with water (20 mL) and NaHCO3 (satd aq) (20 mL). The organic layer was dried over Na2SO4, filtered and concentrated to yield a white solid. The crude was filtered through a pile of silica, concentrated, and used in the next step without further purification. The crude residue (344 mg) was dissolved in MeOH/CH2Cl2 (1:1, 6 mL) and NaOMe (1 M, 0.3 mL) was added. After 1.5 h of stirring at rt, AcOH (6 mL) was added and the reaction mixture was concentrated to yield a white solid. HPLC gave 2a after lyophilization as a white solid (33 mg, 11%).
  • 47
  • [ 1592-38-7 ]
  • [ 124-40-3 ]
  • [ 13577-85-0 ]
YieldReaction ConditionsOperation in experiment
95% With oxygen; sodium hydroxide In water at 25℃; for 24h; Green chemistry;
87% With oxygen; sodium hydroxide In water; <i>tert</i>-butyl alcohol at 25℃; for 24h; General procedure for the amidation using Au/HAP catalyst General procedure: Unless otherwise noted, reactions were carried out as following: a mixture of alcohol 1 (1.00mmol, 2.0 equiv), amine 2 (0.50 mmol), sodium hydroxide (0.50 mmol) and Au/HAP (45 mg, 1.69wt%) were vigorously stirred in 0.5 mL H2O at 40 °C for 24 h under oxygen balloon. After completion of the reaction, the mixture is cooled to room temperature, diluted with ethyl acetate. The catalyst was separated by centrifugation and washed with ethyl acetate (3 x 15.0 mL). The combined organic layer was washed by saturated NaCl solution and dried over anhydrous magnesium sulfate and the solvent was removed under vacuum. The residue was purified by flash chromatography on a short silica gel (eluent: petroleum ether/ethyl acetate = 10:1, 2:1, or 1:1) toafford the corresponding amide 3.
  • 48
  • [ 1592-38-7 ]
  • [ 56844-12-3 ]
  • 6-bromo-4-(naphthalen-2-ylmethoxy)thieno[2,3-d]pyrimidine [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% With caesium carbonate; In acetonitrile; for 6h;Inert atmosphere; Reflux; General procedure: 6-Bromo-4-chlorothieno[2,3-d]pyrimidine(5a) (200 mg, 0.802 mmol) was mixed with 1-phenylethanol (2a) (118 mg, 0.962 mmol), Cs2CO3( 313 mg, 0.962 mmol) and acetonitrile (2 mL). The reaction was then stirredunder nitrogen atmosphere at reflux and followed by GC. The mixture was cooledto rt, diluted with EtOAc (40 mL), washed with sat. aq. KHCO3 (20mL), water (2×20 mL) and brine (30 mL). The combined organic fractions weredried over Na2SO4 and concentrated in vacuum. Crudeproduct was absorbed onto Celite 545 and purified by silica gel columnchromatography (n-pentane/EtOAc,6/1). This gave 245 mg (0.730 mmol, 91%) of 6a as an off-white solid.
  • 49
  • [ 1592-38-7 ]
  • [ 28144-70-9 ]
  • [ 18818-43-4 ]
YieldReaction ConditionsOperation in experiment
84% With tert.-butylhydroperoxide In dimethyl sulfoxide at 110℃; for 12h;
84% With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; tetrabutylammonium perchlorate; toluene-4-sulfonic acid In acetonitrile at 20℃; for 16.5h; Electrolysis;
83% With tert.-butylhydroperoxide In dimethyl sulfoxide at 25 - 35℃; for 40h; Irradiation; Green chemistry; 1. General information. General experimental procedure for the synthesis of quinazolinones: General procedure: a 10-mL glass tube was filled with the required 2-aminobenzamide (0.2 mmol), alcohol (0.5 mmol), and TBHP (1 equiv.) and irradiated at room temperature with an 18 W blue LED for 40 h. After reaction completion (monitored by TLC), water was added to the reaction solution and the mixture was extracted with EtOAc. The combined organic layers were dried over anhydrous Na2SO4, and concentrated under reduced pressure. The crude product was purified by silica-gel column chromatography using petroleum ether/ethyl acetate as eluent to give the desired product.
81% With Iron(III) nitrate nonahydrate; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen; potassium hydroxide In toluene at 100℃; for 12h;
75% With tert.-butylhydroperoxide; zinc(II) iodide In water; dimethyl sulfoxide at 110℃; for 16h;
72% With oxygen In dimethyl sulfoxide at 120℃; for 12h; Schlenk technique; Sealed tube; Green chemistry; General procedure for the synthesis of N-heterocyclic compounds General procedure: A 25 mL Schlenk-type tube equipped with a magnetic stir bar was charged with o-substituted aniline 1a-1f. The reaction tube was evacuated and back-filled with O2. Under oxygen atmospheres, ethers or alcohols 2a-2n and DMSO were added at room temperature, then the reaction mixture was stirred at 120 C for 12 h. The reaction was monitored by TLC. After completion of the reaction, the resulting solution was cooled to room temperature, and neutralized with saturated NaHCO3 aqueous solution. The product was extracted with EtOAc or CHCl3, dried over anhydrous Na2SO4 and concentrated in vacuum. The crude product was purified by flash column chromatography on silica gel to give N-heterocyclic compounds 3.
69% With potassium <i>tert</i>-butylate; C37H30N3OPPd In toluene at 110℃; for 24h;
59% With C35H33ClN3O2PPd; potassium hydroxide In m-xylene at 110℃; for 24h;

  • 50
  • [ 1592-38-7 ]
  • [ 55-21-0 ]
  • N-(naphthalen-2-ylmethyl)benzamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% With C44H39IrN2P(1+)*C32H12BF24(1-); Cs2CO3 In toluene at 120℃; for 3h; Inert atmosphere;
88% With bis[dichlorido(η5-1,2,3,4,5-pentamethyl-cyclopentadienyl)iridium(III)]; Cs2CO3 In toluene at 130℃; for 12h; 11 N-(4-(trifluoromethoxy)benzyl)benzamide The benzonitrile (103mg, 1mmol), [(IPr) AuNTf] (17mg, 0.02mmol, 2mol%),tetrahydrofuran (0.5ml), H 2O (0.5ml) were successively added to the reaction flask25mlSchlenk. After the mixture was reacted at 130°C at 12 hours, cooled to roomtemperature, the solvent was removed in vacuo under reduced pressure. The [Cp * IrCl 2]2(8mg, 0.01mmol, 1mol%), 2- naphthalene-methanol (190mg, 1.2mmol), cesium carbonate(65mg, 0.2equiv.) And toluene (1ml) was added to the reaction flask and the reactionmixture was continued at 130°C at 12 hours, cooled to room temperature. The solvent wasremoved rotary evaporation, then purified by column chromatography (developing solvent:ethyl acetate / petroleum ether) to give pure title compound Yield: 88%.
81% With C23H24ClIrN3OS(1+)*F6P(1-); Cs2CO3 In toluene at 120℃;
64% With Cs2CO3 In toluene at 40℃; for 48h; Inert atmosphere;
214 mg With Cs2CO3 In toluene at 130℃; for 12h; Inert atmosphere; Schlenk technique;
With bis[dichlorido(η5-1,2,3,4,5-pentamethyl-cyclopentadienyl)iridium(III)]; Cs2CO3 In toluene at 130℃; for 12h;

  • 51
  • [ 628-02-4 ]
  • [ 1592-38-7 ]
  • naphthalen-2-ylmethyl hexanoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% With scandium tris(trifluoromethanesulfonate) In n-heptane at 100℃; for 24h; General Procedure 2. N-Acylation of Alcohols with Amides: General procedure: An oven dried Radleys carousel tube was charged with amide species (2 mmol),Sc(OTf)3 (5 mol%, 49.3 mg) and n-heptane(2.0 mL), followed by the alcohol species (2.4 mmol). The reaction was then heated with stirring at either 100 or 125 oC (see Table 2 or Table3) for 24 hours with the tap open. After being allowed to cool to room temperature the solvent was removed in vacuo on a rotary evaporator and the crude reaction mixture was were analyzed by their 1H NMR spectra. Afterwhich the crude reaction was purified using a 20mm x 50mm plug of silica geland eluting with DCM or by column chromatography.
  • 52
  • [ 1592-38-7 ]
  • [ 6638-79-5 ]
  • [ 113443-62-2 ]
YieldReaction ConditionsOperation in experiment
83% With tert.-butylhydroperoxide; copper(II) acetate monohydrate; calcium carbonate; In acetonitrile; at 80℃; for 24h; General procedure: An oven-dried 15 mL glass vial with a magnetic stirrer bar was charged with Cu(OAc)2·H2O (12 mg, 6 mol%), N,O-dimethylhydroxylamine hydrochloride (2; 117 mg, 1.2 mmol), the respective benzyl alcohol 1 (1 mmol), aq 70% TBHP (0.17 mL, 1.2 mmol), CaCO3 (120 mg, 1.2 mmol) in MeCN (1 mL). The glass vial was flushed with N2 three times and the contents were stirred at r.t. for 1 h. Then the reaction mixture was stirred for 24 h at 80 C. After completion of the reaction, the mixture was cooled to r.t. All volatiles were removed under vacuum. The product was extracted with EtOAc (20 mL) and the organic layer was washed with sat. aq NaHCO3 (20 mL), dried (Na2SO4), and the solvent removed under vacuum. The Weinreb amide product 3 was purified by column chromatography (silica gel, 100-200 mesh) using a gradient of petroleum ether (bp 60-80 C) and EtOAc. All the amides were identified by GC-MS, 1H, and 13C NMR spectroscopic analysis.
  • 53
  • [ 1592-38-7 ]
  • [ 448-59-9 ]
  • 2-(4-fluorobenzyl)naphthalene [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran
  • 55
  • [ 67-71-0 ]
  • [ 1592-38-7 ]
  • [ 939-27-5 ]
YieldReaction ConditionsOperation in experiment
77% With platinum on carbon; potassium <i>tert</i>-butylate; hydrogen In toluene for 24h; Inert atmosphere; Reflux;
71% With C24H20ClN2OPRu; potassium <i>tert</i>-butylate; hydrogen In tetrahydrofuran at 125℃; for 20h;
  • 56
  • [ 136-95-8 ]
  • [ 1592-38-7 ]
  • N-(naphthalen-2-ylmethyl)benzo[d]thiazol-2-amine [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With sodium hydroxide at 100℃; for 24h; Sealed tube; Green chemistry;
77% With C50H38ClN3O2P2RuS; potassium hydroxide In toluene at 100℃; for 12h; 4.3. Typical procedure for N-alkylation of aromatic amines with alcohols General procedure: A 10 mL round-bottomed flask, with a stirring bar, was charged with 1-mol % of ruthenium(II) catalyst, 1 mmol of amine, 1.2 mmol of alcohol, 4 mmol of KOH and 3 mL of toluene. The reaction mixture was heated at 100 °C with stirring for 10 h on an oil bath. Upon completion (as monitored by TLC), the reaction mixture was cooled to room temperature, quenched with water (3 mL) and the organic products were extracted with ethyl acetate (3×10 mL). The combined organic layers were dried over anhydrous sodium sulphate; passed through a pad ofcelite using ethyl acetate and concentrated by rotary evaporator to afford the crude organic product. This product was purified by using preparative thin layer chromatography using 5% ethyl acetate-hexane susing as the eluent. The product conversion was determined by GC whereas a few representative compounds were characterized by 1HNMR spectroscopy (see Figs. S40-S44; Supplementary Information). The reported isolated yields are an average of two runs.
  • 57
  • [ 354-08-5 ]
  • [ 1592-38-7 ]
  • naphthalen-2-ylmethyl 2-bromo-2,2-difluoroacetate [ No CAS ]
  • 58
  • [ 504-29-0 ]
  • [ 1592-38-7 ]
  • N-(naphthalen-2-ylmethyl)pyridin-2-amine [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With sodium hydroxide at 150℃; for 24h; Schlenk technique; N-(Naphthalen-2-ylmethyl)pyridin-2-amine General procedure: The mixture of benzyl alcohol (1a, 0.3244 g, 3.0 mmol,1.5 equiv.), 2-aminopyridine (6a, 0.1882 g, 2.0 mmol), and NaOH (0.0400 g, 1.0 mmol, 50 mol%)was sealed under air in a 20 mL Schlenk tube and then stirred at 150 oC for 24 h. After completion,the reaction was monitored by TLC and/or GC-MS (>99% GC conversion) and the crude productwas purified by column chromatography using ethyl acetate and petroleum ether as eluent. Thetarget product 7a was obtained in 89% isolated yield. White solid. 1H NMR (500 MHz, CDCl3): δ 8.11(dd, J = 5.0 Hz, J = 1.5 Hz, 1H), 7.83-7.81 (m, 4H), 7.48-7.43 (m, 3H), 7.41-7.37 (m, 1H), 6.59 (ddd,J = 7.0 Hz, J = 5.0 Hz, J = 1.0 Hz, 1H), 6.39 (d, J = 8.5 Hz, 1H), 5.07 (b, 1H), 4.66 (d, J = 6.0 Hz,2H). 13C NMR (125.4 MHz, CDCl3): δ 158.6, 148.1, 137.5, 136.6, 133.4, 132.7, 128.4, 127.70,127.65, 126.1, 125.72, 125.71, 125.6, 113.2, 106.8, 46.4. MS (EI): m/z (%) 234 (90), 233 (96), 141(100), 129 (33), 115 (74), 78 (44). HRMS Calcd for C16H15N2 (M+H), 235.1230; found: 235.1221.
75% With palladium diacetate; sodium 3-(diphenylphosphanyl)benzenesulfonate In water at 120℃; for 16h; Sealed tube;
75% With C50H38ClN3O2P2RuS; potassium hydroxide In toluene at 100℃; for 12h; 4.3. Typical procedure for N-alkylation of aromatic amines with alcohols General procedure: A 10 mL round-bottomed flask, with a stirring bar, was charged with 1-mol % of ruthenium(II) catalyst, 1 mmol of amine, 1.2 mmol of alcohol, 4 mmol of KOH and 3 mL of toluene. The reaction mixture was heated at 100 °C with stirring for 10 h on an oil bath. Upon completion (as monitored by TLC), the reaction mixture was cooled to room temperature, quenched with water (3 mL) and the organic products were extracted with ethyl acetate (3×10 mL). The combined organic layers were dried over anhydrous sodium sulphate; passed through a pad ofcelite using ethyl acetate and concentrated by rotary evaporator to afford the crude organic product. This product was purified by using preparative thin layer chromatography using 5% ethyl acetate-hexane susing as the eluent. The product conversion was determined by GC whereas a few representative compounds were characterized by 1HNMR spectroscopy (see Figs. S40-S44; Supplementary Information). The reported isolated yields are an average of two runs.
  • 59
  • [ 1592-38-7 ]
  • [ 55644-75-2 ]
  • [ 2506-41-4 ]
YieldReaction ConditionsOperation in experiment
26%Spectr.; 65% With chloro-trimethyl-silane; In neat (no solvent); at 70 - 75℃; for 23h;Green chemistry; General procedure: A mixture of alcohol (0.5 mmol) in the case of solids, which had been powedered for 1-2 min and halosilanes (0.55 mmol) was transferred to a 4 mL screw-capped vial, and stirred at rt or heated at 70-75 C for 0.5 h-24 h. The progress of the reaction mixture was monitored by TLC. Upon completion of the reaction, the crude reaction mixture was cooled down to the room temperature and volatile product (TMS)2O was removed by evaporation at 30-35oC under reduced pressure and the remaining was analysed by 1H NMR. Finally, if necessary, the pure final product was obtained after column chromatography on dried silica. Detailed experimental information such as isolated yields, and spectroscopic and other identification data are given in Characterization Data of Isolated Final Products chapter in the SI.
  • 60
  • [ 1592-38-7 ]
  • [ 1527-91-9 ]
  • C31H23N3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% With Cu/OMS-2; In toluene; at 90.0℃; for 20.0h; General procedure: Cu/OMS-2 (10 mg, 0.25 mol%), benzyl alcohol (2 mmol), N-arylamidine (0.5 mmol), toluene (2 mL) were added to a flask with a bar. The flask was stirred at 90 C for 20 h under air. After cooling to room temperature, the mixture was diluted with ethyl acetate and filtered. The filtrate was removed under reduced pressure to get the crude product, which was further purified by silica gel chromatography (petroleum/ethyl acetate = 40/1-50/1 as eluent) to yield corresponding product. The identity and purity of the products were confirmedby 1H, 13C NMR spectroscopic and HRMS analysis.
  • 61
  • [ 1592-38-7 ]
  • [ 141-78-6 ]
  • [ 35480-23-0 ]
YieldReaction ConditionsOperation in experiment
94% With C16H25N3O2S for 24h; Molecular sieve; Reflux;
94% With C16H25N3O2S for 24h; Reflux; Molecular sieve;
92% Stage #1: 2-Naphthalenemethanol With potassium <i>tert</i>-butylate In dimethyl sulfoxide at 20℃; for 0.166667h; Inert atmosphere; Stage #2: ethyl acetate In dimethyl sulfoxide at 20℃; for 0.166667h; Inert atmosphere; 2.2 General procedure for the acetylation of alcohols General procedure: The alcohol (0.5 mmol) and KOtBu (1.0 mmol) were taken in a two-neck round bottomed flask and then purged with nitrogen gas. Then 2 mL of dimethylsulphoxide (DMSO) was added to it and the reaction mixture was stirred at room temperature for 10 min. Then 1.0 mL of EtOAc was added to it and the stirring was contunued for an additional 10 minutes. After completion of the reaction, the reaction mixture was diluted with water and extracted with ethyl acetate (3 x 20 mL). The combined organic layer was washed with brine, dried over anhydrous Na2SO4, evaporated under reduced pressure. Then the crude product was purified by column chromatography using silica gel (60-120 mesh) and hexane/EtOAc as eluent. Naphthalen-2-ylmethyl acetate (3a): According to the GP-2 the substrate naphthalene-2-ylmethanol afforded the product naphthalene-2-ylmethyl acetate (4a) as a white solid; 1H NMR (200 MHz,Chloroform-d) δ: 7.95-7.72 (m, 4H), 7.45-7.53 (m, 3H), 5.29 (s, 2H), 2.15 (s,3H); 13C NMR (50 MHz, Chloroform-d) δ: 171.05, 133.5, 133.4, 133.3, 128.54, 128.1, 127.9, 127.5, 126.5, 126.4, 126.1, 66.60, 21.19. Spectral data are in well agreement with the literature reported data.
  • 62
  • [ 1592-38-7 ]
  • [ 21658-35-5 ]
  • [ 85-08-5 ]
  • 63
  • [ 1592-38-7 ]
  • [ 98-86-2 ]
  • 3-(naphthalen-2-yl)-1-phenylpropan-1-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% With bis[dichlorido(η5-1,2,3,4,5-pentamethyl-cyclopentadienyl)iridium(III)]; 2-(2-(diphenylphosphanyl)phenyl)benzo[d]oxazole; potassium hydroxide In toluene at 110℃; for 24h; Schlenk technique; Inert atmosphere; 4.3. General procedure for alkylation reactions General procedure: [Cp*IrCl2]2 (1 mol %, 0.01 mmol, 8.0 mg), 4a (2 mol %, 0.02 mmol,7.6 mg), KOH (10 mol %, 0.1 mmol, 5.6 mg), and toluene (5 mL) wereadded to a 25mL Schlenk tube with stirring under N2 at roomtemperature. Then ketones/secondary alcohols/amines (1 mmol),primary alcohols (1.1 mmol) were added by syringe. The reactionmixture was heated to 110 °C under reflux in an oil bath for 24 h. Itwas cooled to ambient temperature. Then it was concentrated invacuo, and purified by flash column chromatography with petroleumether/ethyl acetate to afford the corresponding alkylatedproduct.
92% With dimanganese decacarbonyl; sodium hydroxide In toluene at 110℃; for 2h; Inert atmosphere; Glovebox; Sealed tube;
90% With [Ru(η6-p-cymene)Cl2]2; Cs2CO3; 2-((diphenylphosphino)amido)pyridine In toluene at 120℃; for 18h; Schlenk technique; Inert atmosphere; General procedure for the [RuCl26-p-cymene)]2/L1-catalyzed α-alkylation of ketones with alcohols General procedure: Cs2CO3 (0.6 mmol,195.6 mg) and toluene (1 mL) were added to a Schlenk tube under a N2 atmosphere. [RuCl2(η6-p-cymene)]2 (0.005 mmol, 3.1 mg), L1 (0.01 mmol, 2.8 mg), alcohols (1.1 mmol) and ketones (1.0 mmol) were added in that order and the Schlenk tube was closed and stirred at 120°C for 18 h. The reaction mixture was cooled to room temperature, quenched with water and extracted with ethyl acetate (20 mL x 3). The combined extracts were dried over anhydrous sodium sulfate and concentrated in vacuo. The product was purified by column chromatography using petroleum ether/ethyl acetate as eluent to give the corresponding product (Figs. S22-S47 in Supporting Information).
88% With C23H41MnNO2P2; potassium-t-butoxide In toluene at 125℃; for 18h; Schlenk technique;
85% With samarium diiodide; potassium-t-butoxide In tetrahydrofuran; toluene at 140℃; for 1h; Microwave irradiation; Inert atmosphere;
82% With bis(μ-chloro)-bis[1,3-di(2-pyridyl)-4,6-dimethylbenzene-N,C(2'),N-iridium chloride]; Cs2CO3 In tert-Amyl alcohol for 12h; Reflux;
82% With C38H36Cl4Ir2N4; Cs2CO3 In tert-Amyl alcohol for 12h; Reflux; 12 Example 12: 3-(naphthalen-2-yl)-1-phenylpropan-1-one A mixture of acetophenone (60 mg, 0.5 mmol), cat.1 (5.4 mg, 0.005 mmol, 1.0 mol%),Cesium carbonate (33 mg, 0.1 mmol, 0.2 equiv.),2-naphthalene methanol (95 mg, 0.6 mmol)And tert-amyl alcohol (1 ml) were successively added to a 5 mL round bottom flask.The reaction mixture was refluxed in air for 12 hours,Cool to room temperature.Rotate the solvent to remove the solvent,The purified title compound was then purified by column chromatography (developing solvent: petroleum ether / ethyl acetate)Yield: 82%
82% With [(Cp*IrCl)2(thbpym)][Cl]2; potassium hydroxide In water monomer at 100℃; for 12h; Green chemistry;
78% With C26H28ClIrN4O; potassium hydroxide In toluene at 130℃; for 0.5h;
73% With Mn(7-hydroxy-2-methyl-1,8-naphthyridine-N-oxide)(CO)<SUB>3</SUB>Br; potassium hydroxide In toluene at 130℃; for 0.75h; Sealed tube;
With C51H41N3O2P2RuS; potassium-t-butoxide In toluene at 130℃; for 0.5h; Schlenk technique; Inert atmosphere;
Stage #1: 2-Naphthalenemethanol With 1,10-Phenanthroline; potassium-t-butoxide; nickel(II) bromide Inert atmosphere; Schlenk technique; Stage #2: acetophenone In toluene at 140℃; for 36h; Inert atmosphere; Schlenk technique;

Reference: [1]Huang, Shuang; Wu, Si-Peng; Zhou, Quan; Cui, He-Zhen; Hong, Xi; Lin, Yue-Jian; Hou, Xiu-Feng [Journal of Organometallic Chemistry, 2018, vol. 868, p. 14 - 23]
[2]Lan, Xiao-Bing; Ye, Zongren; Huang, Ming; Liu, Jiahao; Liu, Yan; Ke, Zhuofeng [Organic Letters, 2019, vol. 21, # 19, p. 8065 - 8070]
[3]Liu, Shi-Yuan; Xu, Lin-Yan; Liu, Chun-Yu; Ren, Zhi-Gang; Young, David James; Lang, Jian-Ping [Tetrahedron, 2017, vol. 73, # 17, p. 2374 - 2381]
[4]Chakraborty, Subrata; Daw, Prosenjit; Ben David, Yehoshoa; Milstein, David [ACS Catalysis, 2018, vol. 8, # 11, p. 10300 - 10305]
[5]Pawar, Gaurav; Mahammad Ghouse, Shaik; Kar, Swayamsiddha; Manohar Chelli, Sai; Reddy Dannarm, Srinivas; Gour, Jitendra; Sonti, Rajesh; Nanduri, Srinivas [Chemistry - An Asian Journal, 2022, vol. 17, # 8]
[6]Liu, Pengcheng; Liang, Ran; Lu, Lei; Yu, Zhentao; Li, Feng [Journal of Organic Chemistry, 2017, vol. 82, # 4, p. 1943 - 1950]
[7]Current Patent Assignee: NANJING UNIVERSITY OF SCIENCE AND TECHNOLOGY - CN106478395, 2017, A Location in patent: Paragraph 0080; 0081; 0082; 0083; 0084
[8]Meng, Chong; Xu, Jing; Tang, Yawen; Ai, Yao; Li, Feng [New Journal of Chemistry, 2019, vol. 43, # 35, p. 14057 - 14065]
[9]Kaur, Mandeep; U Din Reshi, Noor; Patra, Kamaless; Bhattacherya, Arindom; Kunnikuruvan, Sooraj; Bera, Jitendra K. [Chemistry - A European Journal, 2021, vol. 27, # 41, p. 10737 - 10748]
[10]Bera, Jitendra K.; Laskar, Roshayed Ali; Nath, Anubhav; Patra, Kamaless [Organometallics, 2022]
[11]Zhang, Chong; Zhao, Jiong-Peng; Hu, Bowen; Shi, Jing; Chen, Dafa [Organometallics, 2019, vol. 38, # 3, p. 654 - 664]
[12]Cao, Yuanjie; Chen, Tieqiao; Huang, Tianzeng; Liu, Long [New Journal of Chemistry, 2020, vol. 44, # 21, p. 8697 - 8701]
  • 64
  • [ 1592-38-7 ]
  • [ 13323-81-4 ]
  • 3-(naphthalen-2-yl)-1-phenylpropan-1-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% With chlorine[2-(4,5-dihydro-1H-imidazol-2-yl)-6-methoxypyridine](pentamethylcyclopentadienyl)iridium(III) chloride; potassium hydroxide In water at 80℃; for 16h; Schlenk technique; Inert atmosphere; chemoselective reaction;
92% With C30H43ClCoN2P3(1+)*Cl(1-); potassium <i>tert</i>-butylate In toluene at 125℃; for 24h; Inert atmosphere; Glovebox;
90% With C16H13MnN5O3(1+)*Br(1-); sodium hydroxide In tert-Amyl alcohol at 110℃; for 6h; Green chemistry;
86% With C27H42ClN2PRu; caesium carbonate In 5,5-dimethyl-1,3-cyclohexadiene at 150℃; for 48h; Inert atmosphere; Glovebox; Sealed tube;
82% With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; 2-(2-(diphenylphosphanyl)phenyl)benzo[d]oxazole; potassium hydroxide In toluene at 110℃; for 24h; Schlenk technique; Inert atmosphere; 4.3. General procedure for alkylation reactions General procedure: [Cp*IrCl2]2 (1 mol %, 0.01 mmol, 8.0 mg), 4a (2 mol %, 0.02 mmol,7.6 mg), KOH (10 mol %, 0.1 mmol, 5.6 mg), and toluene (5 mL) wereadded to a 25mL Schlenk tube with stirring under N2 at roomtemperature. Then ketones/secondary alcohols/amines (1 mmol),primary alcohols (1.1 mmol) were added by syringe. The reactionmixture was heated to 110 °C under reflux in an oil bath for 24 h. Itwas cooled to ambient temperature. Then it was concentrated invacuo, and purified by flash column chromatography with petroleumether/ethyl acetate to afford the corresponding alkylatedproduct.

  • 65
  • [ 1592-38-7 ]
  • [ 4559-70-0 ]
  • diphenyloxophosphinyl(naphthalen-2-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With dipotassium peroxodisulfate In N,N-dimethyl-formamide at 30℃; 16.1; 16.2; 16.3 Example 16: Synthesis of Diphenylphosphinylidene (naphthalene-2-yl) methanol (1) β-naphthalene methanol (0.079 g, 0.5 mmol) was added to the reaction flask,Diphenylphosphine oxide (0.152 g, 0.75 mmol),Potassium persulfate (0.270 g, 1.0 mmol) and N, N- dimethylformamide (2 mL),30 ° C reaction; (2) TLC tracking reaction until complete; (3) The crude product obtained after the completion of the reaction was separated by column chromatography (dichloromethane: methanol = 40: 1)The target product was obtained (yield 85%).
  • 66
  • [ 1592-38-7 ]
  • [ 140-29-4 ]
  • [ 201015-09-0 ]
YieldReaction ConditionsOperation in experiment
87% With potassium <i>tert</i>-butylate; C35H27Cl2N4PRuS In toluene at 135℃; for 1h; Inert atmosphere; Schlenk technique;
82% With C32H25Cl2N6O2Rh2(1+)*Cl(1-); sodium hydroxide In toluene at 110℃; for 24h; Sealed tube; Inert atmosphere; chemoselective reaction;
75% With C18H13BrMnN3O3S; potassium <i>tert</i>-butylate In tert-Amyl alcohol at 140℃; for 24h; Inert atmosphere;
72% With potassium <i>tert</i>-butylate; cobalt(II) chloride; 1,2-bis-[(2,6-diisopropylphenyl)imino]acenaphthene In toluene at 150℃; for 36h; Green chemistry; chemoselective reaction;

  • 67
  • [ 1592-38-7 ]
  • [ 20176-11-8 ]
YieldReaction ConditionsOperation in experiment
84% With tert.-butylhydroperoxide; tetrabutyl phosphonium bromide In water; chlorobenzene at 80℃; for 3h; Sealed tube; General procedure for the synthesis of benzoic anhydride (2a) General procedure: In a 5 mL sealed tube, TBPB(30 mol%, 0.041 g), and TBHP (70 wt% in H2O, 1.0 mmol, 0.131 g) was added to a solution ofbenzyl alcohol 1a (0.4 mmol, 0.043 g) in chlorobenzene (1 mL). The resultant mixture washeated at 80 °C for 2.5 h. After completion of the reaction as was indicated by TLC monitoring,the reaction mixture was cooled to ambient temperature and saturated NaHCO3 (2 mL) wasadded. The product was extracted with ethyl acetate (2 × 3 mL). The combined organic phasewas dried over Na2SO4. The solvent was removed under the reduced pressure. The residue waspurified by column chromatography using n-hexane-EtOAc (15:1) as eluent to afford pureproduct 2a as a white solid.
  • 68
  • [ 1592-38-7 ]
  • [ 6048-29-9 ]
  • (2E)-1-phenyl-3-(2-naphthyl)-2-propen-1-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% With [2,2]bipyridinyl; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium hydroxide; copper(ll) bromide In formamide; acetonitrile at 65℃; for 24h; Schlenk technique; diastereoselective reaction; α,β-Unsaturated Esters 3, α,β-Unsaturated Ketones 4, and α,β-Unsaturated Nitriles 5; General Procedure General procedure: Alcohol (1 mmol), phosphonium salt (1.1 mmol), NaOH (1.1 mmol),CuBr2 (5 mol%), 2,2′-bipy (5 mol%), and TEMPO (5 mol%) were mixed in MeCN and HCONH2 (1:1, 2 mL) in a 100-mL Schlenk tube with an air balloon, and the mixture was stirred at 65 °C for 24 h (monitoring by TLC and/or GC-MS). After completion, product was purified by column chromatography (EtOAc and petroleum ether).
  • 69
  • [ 1592-38-7 ]
  • [ 4336-70-3 ]
  • (E)-3-(naphthalen-2-yl)-2-propenenitrile [ No CAS ]
  • (Z)-3-(naphthalen-2-yl)acrylonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
With [2,2]bipyridinyl; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium hydroxide; copper(ll) bromide; In formamide; acetonitrile; at 65℃; for 24h;Schlenk technique; General procedure: Alcohol (1 mmol), phosphonium salt (1.1 mmol), NaOH (1.1 mmol),CuBr2 (5 mol%), 2,2?-bipy (5 mol%), and TEMPO (5 mol%) were mixed in MeCN and HCONH2 (1:1, 2 mL) in a 100-mL Schlenk tube with an air balloon, and the mixture was stirred at 65 C for 24 h (monitoring by TLC and/or GC-MS). After completion, product was purified by column chromatography (EtOAc and petroleum ether).
  • 70
  • potassium cyanide [ No CAS ]
  • [ 1592-38-7 ]
  • [ 7498-57-9 ]
YieldReaction ConditionsOperation in experiment
76% Stage #1: 2-Naphthalenemethanol With thionyl chloride at 50℃; Inert atmosphere; Stage #2: potassium cyanide In ethanol at 50℃; for 3h; Inert atmosphere; 3 4.3 Experimental procedure and spectroscopic data for 2-naphthylacetonitrile (8) A mixture of 2-naphthylmethanol 6 (1 g, 6.3 mmol) and SOCl2 (15 mL) was stirred overnight at 50 °C. After removing the excess of SOCl2 under vacuum, 10 mL of ethanol were added and the mixture was stirred for 15 min at room temperature. Then, 6 mL of a potassium cyanide solution (6 M) were added and the mixture was stirred vigorously at 50 °C for 3 h and then poured into 50 mL of water and stirred for 30 min. The precipitate formed was recovered by filtration on fritted glass to give 0.8 g (76%) of the desired product 8 as a white solid. m.p = 82-84 °C; 1H NMR (300 MHz, CDCl3): δ (ppm): 3.91 (s, 2H, CH2); 7.38 (dd, J1 = 1.5 Hz, J2 = 8.4 Hz, 1H); 7.53-7.55 (m, 2H); 7.84-7.89 (m, 4H); 13C NMR (75 MHz, CDCl3): δ (ppm): 23.26 (CH2); 117.14 (CN); 124.90 (C-H); 125.97 (C-H); 126.25 (C-H); 126.36 (C-H); 126.79 (C-H); 127.19 (C); 127.22 (CH); 128.54 (C-H); 132.31 (C); 132.93 (C).
  • 71
  • [ 2834-05-1 ]
  • [ 1592-38-7 ]
  • C22H29BrO2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: 11-bromoundecanoic acid With thionyl chloride In toluene for 5h; Reflux; Enzymatic reaction; Stage #2: 2-Naphthalenemethanol With triethylamine In tetrahydrofuran at 20℃; for 4h; General procedure: SOCl2 (7 mL) wasadded into a solution of 11-bromoundecanoic acid (2.69 g, 10.0 mmol) in drytoluene (10 mL), and then the mixture was refluxed for 5 h. The solvent wasremoved under reduced pressure, and re-dissolved by dry tetrahydrofuran (THF, 5mL). It was added dropwise into a solution of 9-anthracenylmethanol (2.00 g,9.6 mmol) and triethylamine (TEA, 1.5 mL) in dry THF (20 mL), and then themixture was stirred at room temperature for 4 h. Afterthat, the solvent was removed under reduced pressure, and re-dissolved bydichloromethane. The organic layer was washed by water, brine, dried withsodium sulfate, filtered, and followed by the removal of the solvent undervacuum. Finally, the crude wasdissolved in pyridine (10 mL), and the mixturewas stirred at 50 oC for 6 h. The solvent was removed under reducedpressure, and re-dissolved by methanol. The methanol solution precipitated inether, and the precipitates were filtered and dried to afford a yellow solid, 9-AP-10. The synthesis of 1-BP-10, 2-NP-10, 2-AP-10, and 1-PP-10were carried out by the same methodof 9-AP-10.The difference wasthat 1-phenylmethanol,2-naphthalenylmethanol, 2-anthracenylmethanol, and 1-pyrenylmethanol were used insteadof 9-anthracenylmethanol, respectively.
  • 72
  • [ 867062-95-1 ]
  • [ 1592-38-7 ]
  • naphthalen-2-ylmethyl-1-(9H-fluoren-9-yl)-3-oxo-2,7,10,13-tetraoxa-4-azahexadecan-16-oate [ No CAS ]
  • 73
  • [ 867062-95-1 ]
  • [ 1592-38-7 ]
  • naphthalen-2-ylmethyl 3-(2-(2-(2-aminoethoxy)ethoxy)ethoxy)propanoate trifluoroacetic acid [ No CAS ]
  • 74
  • [ 1592-38-7 ]
  • [ 62-53-3 ]
  • [ 18263-29-1 ]
YieldReaction ConditionsOperation in experiment
92% With sodium hydroxide In toluene at 110℃; for 24h; Inert atmosphere;
85% With tetramethyl ammoniumhydroxide In water; toluene at 80℃; for 12h;
63% With Au/Zn0.02Al2O3 In toluene at 60℃; for 12h; 2.2. Catalytic reaction General procedure: Oxidative coupling of alcohols and amines was performed in aWP-TEC-1020HC parallel reactor provided by WATTCASTM (WATTECSLAB EQUIPMENT CO., LTD.). In a typical protocol, 0.5 mmolbenzyl alcohol, 0.75 mmol aniline, 5 mL toluene and 40 mg catalystwere added successively. And then the reaction mixture was stirred (900 rpm) at 60 C under air (1 atm) for 8 h. The tube wasimmediately cooled in ice water and the reaction mixture wasanalysed using a Thermo Scientific TRACE 1310 gas chromatograph(GC) equipped with a flame ionization detector (FID) and a TR-5column (30 m 0.32 mm 0.25 lm). The quantification was carriedout using the external standard method. A series of toluenesolutions in different concentrations of benzyl alcohol, benzaldehydeor benzylideneaniline were used as external standard, respectively.Each reaction was at least repeated twice to guarantee areproducible result. The conversion of benzyl alcohol, the selectivityto alkylamines and the yield of imine were calculated, on thebasis of a carbon balance. For the reusability test, the catalystwas separated by centrifugation (8000 rpm for 10 min), washedthree times in turn with ethanol (100 mL) and water (100 mL),dried at 50 C for 24 h under vacuum, and was used for the nextrun.
62% With cerium(IV) oxide In toluene at 60℃; for 8h;
58 %Chromat. With oxygen In toluene at 60℃; for 24h; Green chemistry;
at 80℃; for 6h;
With MnZr0.5O(y) In toluene at 80℃; for 3h; Green chemistry;

  • 75
  • [ 1592-38-7 ]
  • [ 33252-29-8 ]
  • 6-(naphthalen-2-ylmethoxy)picolinonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
41.5% Naphthalen-2-ylmethanol (0.23 g, 1.4 mmol) was dissolved in THF (4.0 mL), and NaH, 60% in oil (0.032 g, 0.79 mmol) was added. After stirring at room temperature for 10-15 mm, the solution was cooled to 0 C, and a solution ofchloropicolinonitrile (0.10 g, 0.72 mmol) in THF (3.0 mL) was added dropwisevia syringe. The reaction mixture was heated overnight at 66 C. The reaction mixture was partitioned between EtOAc and water. The aqueous layer was reextracted with EtOAc, and combined organic layers were washed with brine, dried over Na2SO4, filtered and evaporated. The residue was purified by flash chromatorgrapy to provide 130A as a white solid (78 mg, 41.5 %). MS (ESI)m/z283.0(M+Na).
  • 76
  • [ 1592-38-7 ]
  • 2-((7-azido-6-((4,5-bis(benzoyloxy)-2-(((4-methoxybenzyl)oxy)methyl)-6-(2,2,2-trichloro-1-iminoethoxy)tetrahydro-2H-pyran-3-yl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-8-yl)oxy)-5-((7-azido-8-((5-((7-azido-8-((4-oxopentanoyl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)oxy)-3,4-bis(benzoyloxy)-6-(((4-methoxybenzyl)oxy)methyl)tetrahydro-2H-pyran-2-yl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)oxy)-6-(((4-methoxybenzyl)oxy)methyl)tetrahydro-2H-pyran-3,4-diyl dibenzoate [ No CAS ]
  • 2-((-7-azido-6-((4,5-bis(benzoyloxy)-2-(((4-methoxybenzyl)oxy)methyl)-6-(naphthalen-2-ylmethoxy)tetrahydro-2H-pyran-3-yl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-8-yl)oxy)-5-((7-azido-8-((5-((7-azido-8-((4-oxopentanoyl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)oxy)-3,4-bis(benzoyloxy)-6-(((4-methoxybenzyl)oxy)methyl)tetrahydro-2H-pyran-2-yl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)oxy)-6-(((4-methoxybenzyl)oxy)methyl)tetrahydro-2H-pyran-3,4-diyl dibenzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% Stage #1: 2-Naphthalenemethanol; 2-((7-azido-6-((4,5-bis(benzoyloxy)-2-(((4-methoxybenzyl)oxy)methyl)-6-(2,2,2-trichloro-1-iminoethoxy)tetrahydro-2H-pyran-3-yl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-8-yl)oxy)-5-((7-azido-8-((5-((7-azido-8-((4-oxopentanoyl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)oxy)-3,4-bis(benzoyloxy)-6-(((4-methoxybenzyl)oxy)methyl)tetrahydro-2H-pyran-2-yl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)oxy)-6-(((4-methoxybenzyl)oxy)methyl)tetrahydro-2H-pyran-3,4-diyl dibenzoate In dichloromethane at 0 - 20℃; for 0.666667h; Molecular sieve; Inert atmosphere; Stage #2: With trimethylsilyl trifluoromethanesulfonate In dichloromethane at 0℃; for 0.5h; Inert atmosphere; 2-((7-azido-6-((4,5-bis(benzoyloxy)-2-(((4-methoxybenzyl)oxy)methyl)-6-(naphthalen-2-ylmethoxy)tetrahydro-2H-pyran-3-yl)o-xy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-8-yl)oxy)-5-((7-azido-8-((5-((7-azido-8-((4-oxopentanoyl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)oxy)-3,4-bis-(benzoyloxy)-6-(((4-methoxybenzyl)oxy)methyl)tetrahydro-2H-pyran-2-yl)oxy)-2-phenylhexahydropyrano[3,2-d[1,3]dioxin-6-yl)oxy)-6-(((4-methoxybenzyl)oxy)methyl)tetrahydro-2H-pyran-3,4-diyl dibenzoate (19) A mixture of imidate 18 (430 g, 0.2 mmol) and 2-naphthalenemethanol (40 mg, 0.3 mmol) was coevaporated with dry toluene (32 mL), dried under vacuum for 30 min. The mixture was dissolved in anhydrous CH2Cl2 (5 mL) and activated 4Å powdered molecular sieves (1.5 g) was added. The reaction was stirred at room temperature under Ar for 30 min. The reaction was then cooled to 0°C and stirred for an additional 10 min. TMSOTf (1 M in CH2Cl2, 20 μL) was added to the reaction dropwise. After 30 min the reaction was quenched with trimethylamine (0.1 mL) and allowed to warm to room temperature. the mixture was filtered and concentrated in vacuo. The residue was purified by column chromatograph eluting with petroleum ether/ethyl acetate as 2:1→1:1 to give compound 19 (350 mg, 74%), as a white foam.
  • 77
  • [ 1592-38-7 ]
  • 5-((7-azido-8-((4-oxopentanoyl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)oxy)-6-(((4-methoxybenzyl)oxy)methyl)-2-(2,2,2-trichloro-1-iminoethoxy)tetrahydro-2H-pyran-3,4-diyl dibenzoate [ No CAS ]
  • 5-((7-azido-8-((4-oxopentanoyl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)oxy)-6-(((4-methoxybenzyl)oxy)methyl)-2-(naphthalen-2-ylmethoxy)tetrahydro-2H-pyran-3,4-diyl dibenzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% Stage #1: 2-Naphthalenemethanol; 5-((7-azido-8-((4-oxopentanoyl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)oxy)-6-(((4-methoxybenzyl)oxy)methyl)-2-(2,2,2-trichloro-1-iminoethoxy)tetrahydro-2H-pyran-3,4-diyl dibenzoate In dichloromethane at 0 - 20℃; for 0.666667h; Molecular sieve; Inert atmosphere; Stage #2: With trimethylsilyl trifluoromethanesulfonate at 0℃; for 0.5h; 5-(7-azido-8-((4-oxopentanoyl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)oxy)-6-(((4-methoxybenzyl)oxy)methyl)-2-(naphthalen-2-ylmethoxy)tetrahydro-2H-pyran-3,4-diyl dibenzoate (26): A mixture of imidate 5 (559 mg, 0.5 mmol) and2-naphthalenemethanol (139 mg, 0.9 mmol) was coevaporated with dry toluene (35 mL), dried under vacuum for 30 min. The mixture was dissolved in anhydrous CH2Cl2 (17 mL) and activated 4Å powdered molecular sieves (5 g) were added. The reaction was stirred at room temperature under Ar for 30 min. The reaction was then cooled to 0° C and stirred for an additional 10 min. TMSOTf (1M in CH2Cl2, 90μL) was added to the reaction dropwise. After 30 min the reaction was quenched with trimethylamine (0.3 mL) andallowed to warm to room temperature. the mixture was filtered and concentrated in vacuo. The residue was purified by columnchromatograph eluting with petroleum ether/ethyl acetate as 2:1 to give compound 26 (420 mg, 84 %), as a white foam.
  • 78
  • [ 1592-38-7 ]
  • 2-(7-azido-6-(4,5-bis(benzoyloxy)-2-((4-methoxybenzyloxy)methyl)-6-(2,2,2-trich-loro-1-iminoethoxy)tetrahydro-2H-pyran-3-yloxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-8-yloxy)-5-(7-azido-8-(4-oxopentanoyloxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yloxy)-6-((4-methoxybenzyloxy)methyl)tetrahydro-2H-pyran-3,4-diyl dibenzoate [ No CAS ]
  • 2-((7-azido-6-(4,5-bis(benzoyloxy)-2-((4-methoxybenzyloxy)methyl)-6-(naphthalen-2-ylmethoxy)tetrahydro-2H-pyran-3-yl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-8-yloxy)-5-(7-azido-8-(4-oxopentanoyloxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yloxy)-6-((4-methoxybenzyloxy)methyl)tetrahydro-2H-pyran-3,4-diyl dibenzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
92% Stage #1: 2-Naphthalenemethanol; 2-(7-azido-6-(4,5-bis(benzoyloxy)-2-((4-methoxybenzyloxy)methyl)-6-(2,2,2-trich-loro-1-iminoethoxy)tetrahydro-2H-pyran-3-yloxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-8-yloxy)-5-(7-azido-8-(4-oxopentanoyloxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yloxy)-6-((4-methoxybenzyloxy)methyl)tetrahydro-2H-pyran-3,4-diyl dibenzoate In dichloromethane at 0 - 20℃; for 0.75h; Molecular sieve; Inert atmosphere; Stage #2: With trimethylsilyl trifluoromethanesulfonate In dichloromethane at 0℃; for 0.5h; Inert atmosphere; 2-(7-azido-6-(4,5-bis(benzoyloxy)-2-((4-methoxybenzyloxy)methyl)-6(naphthalen-2-ylmethoxy)tetrahydro-2H-pyran-3-yl)oxy)-2-phenylhexahydropyrano[3,2-d][1,3]-dioxin-8-yloxy)-5-(7-azido-8-(4-oxopentanoyloxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yloxy)-6-((4-methoxybenzyloxy)methyl)tetrahydro-2H-pyran-3,4-diyldibenzoate (9) A mixture of imidate 8 (240 mg, 0.1 mmol) and 2-naphthalenemethanol (31 mg, 0.2 mmol) was coevaporated with dry toluene (32 mL), dried under vacuum for 30 min. The mixture was dissolved in anhydrous CH2Cl2 (3 mL) and activated 4Å powdered molecular sieves (800 mg) was added. The reaction was stirred at room temperature under Ar for 30 min. The reaction was then cooled to 0°C and stirred for an additional 15 min. TMSOTf (0.1 M in CH2Cl2, 80 μL) was added to the reaction dropwise. After 30 min the reaction was quenched with trimethylamine (0.1 mL) and allowed to warm to room temperature. the mixture was filtered and concentrated in vacuo. The residue was purified by column chromatograph eluting with petroleum ether/ethyl acetate as 3:1→2:1 to give compound 9 (220 mg, 92%), as a white foam.
  • 79
  • [ 1592-38-7 ]
  • [ 87751-69-7 ]
  • (S,E)-2-(((1,3-diphenylallyl)oxy)methyl)naphthalene [ No CAS ]
YieldReaction ConditionsOperation in experiment
97% With bis(η3-allyl-μ-chloropalladium(II)); (S)-2′-(tert-butyl)-7-(diphenylphosphino)-2,3-dihydro-5′H-spiro[indene-1,4′-oxazole]; caesium carbonate In dichloromethane at 0 - 25℃; for 5h; Schlenk technique; Inert atmosphere; enantioselective reaction; 3.4. General Procedure for the Pd-Catalyzed Asymmetric Allylic Etherification General procedure: Ligand L1 (5.0 mg, 4 mol%) and [Pd(C3H5)Cl]2 (2.2 mg, 2 mol%) were dissolved in DCM (1.0 mL)in a Schlenk tube under Ar. After 0.5 h of stirring at room temperature, allylic acetate 2a (0.3 mmol)dissolved in DCM(0.5 mL) was added, followed by alcohol 4 (0.9 mmol) dissolved in DCM(0.5 mL) and Cs2CO3 (195 mg, 0.9 mmol). The mixture was stirred at 0° C for 5 h and then was diluted with CH2Cl2 and washed with saturated NH4Cl (aq). The organic layers were dried over MgSO4 and filtered, andthe solvents were evaporated in vacuo. The residue was purified by flash column chromatography,eluting with petroleum ether and ethyl acetate to aord the corresponding product 5.
  • 80
  • [ 1592-38-7 ]
  • [ 5994-87-6 ]
  • N-(naphthalen-2-ylmethyl)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
99% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox; 4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
92% With potassium hydroxide In toluene at 110℃; for 4h;
  • 81
  • [ 1592-38-7 ]
  • [ 618-39-3 ]
  • C25H17N3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With oxygen In toluene at 110℃; for 20h; Schlenk technique; 2.2 Typical procedure for the synthesis of 1,3,5-triazine 3a General procedure: OMS-2-SH-B (20 mg, 10 mol%), benzyl alcohol (0.3 mmol) and benzamidine (0.5 mmol) were added into a Schlenk tube. Then, air was removed and toluene (1 mL) was added by a syringe under O2 atmosphere. If substituted benzyl alcohol was liquid, it was added with toluene under O2 balloon protection. If methyl benzene was used as substrate instead of benzyl alcohol, it was added as solvent (1 mL) into the reaction tube by syringe under O2 atmosphere. The mixture was stirred for required time at certain temperature for 20 h. The resulting mixture was cooled down, filtered and washed with EtOAc, and concentrated under reduced pressure to give the crude product. Finally, the product was purified by silica gel chromatography to yield the pure product.
  • 82
  • [ 89359-54-6 ]
  • [ 1592-38-7 ]
  • 2-((non-8-en-1-yloxy)methyl)naphthalene [ No CAS ]
YieldReaction ConditionsOperation in experiment
67% General procedure: 4.3.1. ((oct-7-en-1-yloxy)methyl)cyclohexane (H1)To a stirred solution of cyclohexylmethanol (6) (492 muL, 4.0 mmol,2 eq) in DMF (7 mL) under argon was added NaH (60% suspension inmineral oil; 160 mg, 4.0 mmol, 2 eq) at 0 C. The suspension was stirredat 0 C for 30 min, then 8-bromodec-1-octene (7) (336 muL, 2.0 mmol,1 eq) was added dropwise to the mixture. The mixture was allowed towarm to room temperature and stirred for 1 h. After the reaction wasquenched with saturated NH4Cl, the whole was extracted with Et2O.The extract was washed with H2O and brine, then dried over MgSO4.The filtrate was concentrated under reduced pressure to give an oilyresidue, which was purified using silica gel chromatography (petroleum ether:EtOAc=40:1) to afford H1 (341 mg, 76% yield) as a colorless oil.
  • 83
  • [ 1592-38-7 ]
  • [ 104-94-9 ]
  • [ 435274-63-8 ]
YieldReaction ConditionsOperation in experiment
65% With C50H38ClN3O2P2RuS; potassium hydroxide In toluene at 100℃; for 12h; 4.3. Typical procedure for N-alkylation of aromatic amines with alcohols General procedure: A 10 mL round-bottomed flask, with a stirring bar, was charged with 1-mol % of ruthenium(II) catalyst, 1 mmol of amine, 1.2 mmol of alcohol, 4 mmol of KOH and 3 mL of toluene. The reaction mixture was heated at 100 °C with stirring for 10 h on an oil bath. Upon completion (as monitored by TLC), the reaction mixture was cooled to room temperature, quenched with water (3 mL) and the organic products were extracted with ethyl acetate (3×10 mL). The combined organic layers were dried over anhydrous sodium sulphate; passed through a pad ofcelite using ethyl acetate and concentrated by rotary evaporator to afford the crude organic product. This product was purified by using preparative thin layer chromatography using 5% ethyl acetate-hexane susing as the eluent. The product conversion was determined by GC whereas a few representative compounds were characterized by 1HNMR spectroscopy (see Figs. S40-S44; Supplementary Information). The reported isolated yields are an average of two runs.
72 %Spectr. With C30H43ClCoN2P3(1+)*Cl(1-); potassium <i>tert</i>-butylate In toluene at 85℃; for 24h; Inert atmosphere; Glovebox; Sealed tube; Green chemistry;
  • 84
  • [ 1592-38-7 ]
  • [ 14268-66-7 ]
  • C18H15NO2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With C50H38ClN3O2P2RuS; potassium hydroxide In toluene at 100℃; for 12h; 4.3. Typical procedure for N-alkylation of aromatic amines with alcohols General procedure: A 10 mL round-bottomed flask, with a stirring bar, was charged with 1-mol % of ruthenium(II) catalyst, 1 mmol of amine, 1.2 mmol of alcohol, 4 mmol of KOH and 3 mL of toluene. The reaction mixture was heated at 100 °C with stirring for 10 h on an oil bath. Upon completion (as monitored by TLC), the reaction mixture was cooled to room temperature, quenched with water (3 mL) and the organic products were extracted with ethyl acetate (3×10 mL). The combined organic layers were dried over anhydrous sodium sulphate; passed through a pad ofcelite using ethyl acetate and concentrated by rotary evaporator to afford the crude organic product. This product was purified by using preparative thin layer chromatography using 5% ethyl acetate-hexane susing as the eluent. The product conversion was determined by GC whereas a few representative compounds were characterized by 1HNMR spectroscopy (see Figs. S40-S44; Supplementary Information). The reported isolated yields are an average of two runs.
  • 85
  • [ 1592-38-7 ]
  • [ 108-91-8 ]
  • N-(naphthalen-2-ylmethyl)cyclohexanamine [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With C50H38ClN3O2P2RuS; potassium hydroxide In toluene at 100℃; for 12h; 4.3. Typical procedure for N-alkylation of aromatic amines with alcohols General procedure: A 10 mL round-bottomed flask, with a stirring bar, was charged with 1-mol % of ruthenium(II) catalyst, 1 mmol of amine, 1.2 mmol of alcohol, 4 mmol of KOH and 3 mL of toluene. The reaction mixture was heated at 100 °C with stirring for 10 h on an oil bath. Upon completion (as monitored by TLC), the reaction mixture was cooled to room temperature, quenched with water (3 mL) and the organic products were extracted with ethyl acetate (3×10 mL). The combined organic layers were dried over anhydrous sodium sulphate; passed through a pad ofcelite using ethyl acetate and concentrated by rotary evaporator to afford the crude organic product. This product was purified by using preparative thin layer chromatography using 5% ethyl acetate-hexane susing as the eluent. The product conversion was determined by GC whereas a few representative compounds were characterized by 1HNMR spectroscopy (see Figs. S40-S44; Supplementary Information). The reported isolated yields are an average of two runs.
  • 86
  • [ 91-63-4 ]
  • [ 1592-38-7 ]
  • [ 190437-74-2 ]
YieldReaction ConditionsOperation in experiment
83% With Iron(III) nitrate nonahydrate; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; 18-crown-6 ether; potassium <i>tert</i>-butylate; oxygen In tetrahydrofuran at 50℃; for 8h; General Procedures for Iron/TEMPO-Catalyzed Direct Aerobic Oxidative Coupling of Methyl-Substituted N-Heteroazaarenes with Alcohols General procedure: The oxidative olefination reaction was carried out in a 10 mL long-necked, round-bottomed flask equipped with a magnetic stirrer with an oxygen balloon at 50 °C. Typically, 2-methylquinoline (1 mmol, 143.2 mg), phenylmethanol (2.5 mmol, 270.4 mg), TEMPO (0.05 mmol, 7.8 mg), Fe(NO3)3·9H2O (0.05 mmol, 20.2 mg), tBuOK (2 mmol, 224.4 mg) and 18-crown-6 (1 mmol, 264.3 mg) were charged sequentially into the flask with 3 mL THF. The flask was then evacuated under reduced pressure, followed by the attachment of an oxygen balloon. The resulting mixture was stirred at 50 °C. The progress of the reaction was monitored by TLC. Upon completion, the reaction was quenched with water. Ethyl acetate was added to extract the product. The organic layer was washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography (PE/EA= 30:1-10:1) to afford the desired product 3a in 85% yield as white solid, 196.6 mg.
74%