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CAS No. : | 403-41-8 | MDL No. : | MFCD00004515 |
Formula : | C8H9FO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | PSDSORRYQPTKSV-UHFFFAOYSA-N |
M.W : | 140.16 | Pubchem ID : | 73946 |
Synonyms : |
|
Num. heavy atoms : | 10 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.25 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 37.33 |
TPSA : | 20.23 Ų |
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) : | -6.06 cm/s |
Log Po/w (iLOGP) : | 2.01 |
Log Po/w (XLOGP3) : | 1.54 |
Log Po/w (WLOGP) : | 1.97 |
Log Po/w (MLOGP) : | 2.3 |
Log Po/w (SILICOS-IT) : | 2.25 |
Consensus Log Po/w : | 2.02 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.06 |
Solubility : | 1.23 mg/ml ; 0.00877 mol/l |
Class : | Soluble |
Log S (Ali) : | -1.57 |
Solubility : | 3.74 mg/ml ; 0.0267 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -2.51 |
Solubility : | 0.433 mg/ml ; 0.00309 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.49 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P301+P312-P302+P352-P304+P340-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With phosphorus tribromide In dichloromethane at 4 - 20℃; for 4 h; | 1-(4-fluorophenyl)ethanol (1 equiv., 25 g) was taken up in dichloromethane (150 mL), and PBr3 (0.7 equiv., 12 mL) was added dropwise at 4° C. over a period of 20 min. The reaction mixture was stirred for 4 h at room temperature, then added to iced water (200 g) and extracted with dichloromethane (3*100 mL). The combined organic phases were dried over sodium sulphate, concentrated by evaporation in vacuo, and the liquid product (1-bromoethyl)-4-fluorobenzene was obtained (30 g, 83percent yield). |
21.3% | With phosphorus tribromide In chloroform at 70℃; for 72 h; | A solution of 1-(4-fluorophenyl)ethanol (0.455 mL, 3.57 mmol) and phosphoms tribromide (0.673 mL, 7.13 mmol) in CHC13 (10 mL) was heated at 70 °C for 3 d. The reaction mixture was quenched in ice water and diluted in ethyl acetate. The organic layer was separated and washed with water followed by brine, dried over anhydrous sodium sulfate and concentrated in vacuo to get the crudematerial. The cmde product was purified on a silica gel column with Hexanes/CH2C1(2/1) to afford 1-(1-bromoethyl)-4-fluorobenzene (154 mg, 0.758mo1, 21.3 percent) as acolourless oil. ‘H NMR (400 MHz, CHLOROFORM-d) ö 7.49 - 7.40 (m, 2H), 7.09 - 7.00(m, 2H), 5.23 (q, J=7.0 Hz, 1H), 2.06 (d, J=6.8 Hz, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With [(2-(benzoimidazol-2-yl)-6-(3,5-dimethylpyrazol-1-yl)pyridine)RuCl2(PPh3)]; potassium tert-butylate; acetone; In methanol; at 56℃; under 750.075 Torr; for 0.08333330000000001h;Inert atmosphere;Catalytic behavior; | General procedure: The catalyst solutionwas prepared by dissolving complex 3(36.1 mg,0.05mmol) in methanol (5.0 mL).Under a nitrogen atmosphere, the mixture of an alcohol substrate (2.0 mmol) and1.0 mL of the catalyst solution (0.01mmol) in 20mL acetone was stirred at 56 Cfor 10 minutes. tBuOK(22.4mg, 0.2 mmol)was then added to initiate the reaction.At the stated time, 0.1 mL of the reaction mixture was sampled and immediately diluted with 0.5 mL acetone pre-cooled-to-0 C for GC or NMR analysis. After the reaction was complete, the reaction mixture was condensed under reduced pressure and subject to purification by flash silica gel column chromatography to afford the corresponding ketone product, which was identified by comparison with the authentic sample through NMR and GC analysis. |
98% | With basolite C300; 9-azabicyclo<3.3.1>nonane-N-oxyl; oxygen; In 1,2-dichloro-ethane; at 20℃; for 15.0h;Green chemistry; | General procedure: A 15 mm flame-dried test tube, which was equipped with a magnetic stir bar and charged with alcohol (0.5 mmol, in case of solid), HKUST-1 (10 mol %, 0.05 mmol), ABNO (5 mol %, 0.025 mmol), and Cs2CO3 (1.0 equiv, 0.5 mmol), was evacuated and backfilled with oxygen (this process was repeated 3 times). After 0.5 mL of DCE was added, alcohol (0.5 mmol, in case of liquid), and DCE (0.5 mL) were added in sequence. The reaction mixture was stirred for 15 h at room temperature under O2 balloon. The reaction was diluted by adding CH2Cl2 and filtered through celite. The solvent was removed under vacuo. The residue was purified by column chromatography to give the desired product |
96% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; potassium tert-butylate; copper(I) triflate; 5-[(2S)-pyrrolidine-2-yl]-1H-tetrazole; In N,N-dimethyl-formamide; at 25℃; for 1.0h;Catalytic behavior; | 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), t-BuOK (2 mmol, 1 equiv) and DMF (5 ml). The reaction mixture was stirred at 25 C open to air until the completion of the reaction, as monitored by TLC. The mixture was then diluted with CH2Cl2 (20 ml), washed with water, dried over Na2SO4, and evaporated under vacuum to give the crude product, which was purified by column chromatography to give the pure product. |
96% | With bismuth(III) bromide; dihydrogen peroxide; In water; at 70℃; for 0.166667h;Green chemistry; | General procedure: To a solution of the alcohol (1.0 mmol) and hydrogen peroxide(5.0 mmol, 30% aq) was added BiBr3 (10 mol%). The reactionmixture was stirred at 70 C for 10-40 min, and thereaction mixture was extracted with dichloromethane (2 × 5mL). The combined organic layers were washed with saturatedbrine (2 × 5 mL) and dried with anhydrous MgSO4. After evaporationof the solvent, the residue was purified by flash columnchromatography (SiO2; CH2Cl2-hexane, 3:2) to afford the purecarbonyl compound. |
95% | With 2,4,6-trimethyl-pyridine; 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; iodine; sodium hydrogencarbonate; In dichloromethane; water; at 20 - 22℃; for 1.0h; | General procedure: A solution of corresponding alcohol 1a,b,d-al (8 mmol), nitroxide 4a (0.085 g, 0.4 mmol) and compound 6d (0.097 g, 0.8 mmol) in CH2Cl2 (10 mL) was added to a vigorously stirred solution of NaHCO3 (2.016 g, 24 mmol) in water (10 mL) at 20 C. Then I2 (4.06 g, 16 mmol) powder was added in one portion to the formed reaction mixture at vigorous stirring and temperature 20-22 C. The reaction mixture was stirred at 20-22 C for appropriate time (see Table 1 in the article). Then, a saturated solution of sodium thiosulfate was added to the stirred reaction mixture for discoloration. Organic and aqueous phases were separated and the aqueous phase was then extracted with CH2Cl2 (3×5 mL). Organic phase and the extracts were combined and washed subsequently with saturated aqueous solution of NaCl (5 mL), aqueous solutionof HCl (1%) saturated with NaCl (3 mL), and then with water (5 mL). The washed extract was dried with anhydrous Na2SO4 and evaporated to dryness to give crude product, which was then purified by vacuum distillation under argon atmosphere or by recrystallization. |
95% | With 3,3-dichloro-1,2-diphenylcyclopropene; dimethyl sulfoxide; triethylamine; In dichloromethane; at -78 - 20℃;Inert atmosphere; | Place a round bottom flask in a cryogenic coolant circulation tank,Add 3,3-dichloro-1,2-diphenylcyclopropene (8) (522.30 mg, 2 mmol) to the bottle under Ar protection.And 10 ml of dichloromethane,Cool the inside of the bottle to -78 C,Dimethyl sulfoxide (312.52 mg, 4 mmol) was added dropwise.Keep the temperature below -70 C, continue to stir for 30 min after the dropwise addition.Keep the temperature inside the bottle at -78 C - 70 C,<strong>[403-41-8]1-(4-Fluorophenyl)ethanol</strong> (19) (140.16 mg, 1 mmol) was added dropwise.The temperature of the dropping process does not exceed -65 C, and the stirring is continued for 30 min.Add triethylamine (404.76 mg, 4 mmol),Stirring was allowed to return to room temperature and the target product selectivity was 98%.After the reaction, a saturated ammonium chloride solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was combined, washed with saturated NaCI.Obtaining pure 4-heptanone,Colorless liquid, yield 95%. |
93% | With iron(III) sulfate; TEMPOL; oxygen; sodium nitrite; In water; acetonitrile; at 20℃; under 760.051 Torr; for 8.0h; | The oxidation of alcohols was carried out under O2 in a 50-mL two-necked, round-bottom flask equipped with a magnetic stirrer. Typically, Fe2(SO4)3 (0.25 mmol) and TMHPO (0.25 mmol) were added to the flask, followed by 15 mL of a CH3CN/H2O (1:2) solvent mixture. After stirring for 5 min, the alcohol (5 mmol) was added, followed by NaNO2 (0.25 mmol). The resulting mixture was stirred at room temperature and 1 atm pressure of oxygen. When the reactions were completed, the reaction mixture was transferred to a separating funnel and extracted with dichloromethane. The organic layer was dried over anhydrous Na2SO4 and concentrated and further purified by flash chromatography to give the desired product. |
90.1% | With tert.-butylhydroperoxide; at 60℃; for 7.5h; | General procedure: In a typical process, into a 5-ml two-necked round-bottomflask equipped with a magnetic stirrer were addedRu(pbbp)(pydic) (0.002 mmol) and alcohol (2 mmol)successively at room temperature. The mixture washeated to 60 C under stirring, and then TBHP (70%aqueous solution) was slowly dropped in 0.5 h. Thereaction was monitored by GC equipped with a SE 54column (30 m 9 0.5 lm). After reaction, the product waspurified by column chromatography over silica gel (eluent:n-hexane/ethyl acetate) and characterized by 1HNMR. |
88% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; iron(III) trifluoromethanesulfonate; L-isoleucine; oxygen; In 5,5-dimethyl-1,3-cyclohexadiene; for 48.0h;Reflux; Green chemistry; | 0039] H Equipped with a magnetic stirrer in round bottom flask methyl benzyl alcohol (12. 22g, 100. Ommol, namely formula The R1 is 4-methyl, R2 is hydrogen, X is carbon, eta is 1, m is 0), ferric chloride (0. 81g, 5mmol), L- isoleucineAcid (1.31g, 10mmol), TEMP0 (1.56g, 10mmol), toluene 300. OmL was added , then the reaction with oxygen in the air bottleReplacement, stirred and reflux for 6h. After completion of reaction, the reaction mixture was cooled to room temperature, filtered, the filtrate evaporated to give the crude product,The resultant crude product was purified by column chromatography, with n-hexane: Elution: (10 1 volume ratio) mixed liquid of ethyl acetate containing the desired collectionLabeled compound of the eluent, evaporation of the solvent and dried to give the product p-tolualdehyde 10. 93g, 91% yield. 1- (4-fluorophenyl) ethanol (1 · 40g, 10. Ommol, i.e., of formula (I), R1 is 4-fluoro,R2 is methyl, X is carbon, [eta] is l, m is 0) is used, experimental methods and procedures were the same as in Example 1, except that: trifluoromethanesulfonate Iron(0 · 50g, 1. Ommol), L- isoleucine (0 · 26g, 2 · Ommol), TEMPO (0 · 16g, 1 · Ommol), xylene 30. OmL,After stirring at reflux with oxygen reaction bottle of air displacement 48h. To give the final product 1.23g, 88% yield. |
87% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium acetate; (S)-3-phenyl-2-(phenylamino)propionic acid; copper(ll) bromide; In water; for 16.0h;Reflux; Schlenk technique; | General procedure: A mixture of 1-phenethyl alcohol (1.0 mmol), N-(phenyl)phenylalanine(0.0241 g, 0.1 mmol), CuBr2 (0.0223 g, 0.1 mmol),NaOAc (0.1640 g, 2.0 mmol), TEMPO (0.0156 g, 0.1 mmol), andH2O (3.0 mL) were placed into a 100 mL Schlenk tube, whichwas vigorously stirred in air under reflux for 12 h. After thereaction, the product was extracted with CH2Cl2 (3 × 2.0 mL).The combined organic phase was washed with H2O (3.0 mL) anddried over anhydrous MgSO4. After concentration undervacuum, the residue was purified by column chromatography toafford acetophenone.Isolated yield: 0.1080 g (90%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With hydrogen In benzene at 70℃; for 24h; | |
100% | With zirconium(IV) hydrous oxide hydroxide; isopropanol at 130℃; for 0.416667h; | |
100% | With methanol; sodium tetrahydridoborate at 0℃; for 0.75h; |
99.1% | With C55H54Cl4N2O2PRu2; sodium hydroxide In isopropanol at 82℃; for 0.333333h; | |
99% | With methanol; sodium tetrahydridoborate at 4℃; for 1.25h; | 3.j12 1-(4-fluorophenyl)ethanone (1 equiv., 25 g) was dissolved in MeOH (200 mL), NaBH4 (1 equiv., 6.5 g) was added in portions at 4° C. within 45 min, and the mixture was stirred for 30 min. After adding water (100 mL) the reaction mixture was extracted with EE (3*100 mL). The combined organic phases were dried over sodium sulphate. After removing the solvent in vacuo the liquid product 1-(4-fluorophenyl)ethanol was obtained (25 g, 99% yield). |
99% | With C28H36ClF3N2O3RuS; potassium-t-butoxide; isopropanol at 82℃; for 12h; Inert atmosphere; | |
99% | With C53H46ClN3P2Ru; potassium isopropoxide; isopropanol at 82℃; for 0.0166667h; | |
99% | With 1-hydrosilatrane; potassium-t-butoxide In tetrahydrofuran; N,N-dimethyl-formamide at 20℃; for 0.5h; | |
99% | With C25H30ClIrN2O3; lithium hydroxide monohydrate; potassium hydroxide In isopropanol for 2h; Reflux; | |
99% | Stage #1: 1-(4-Fluorophenyl)ethanone With C107H90Cl2N10P4Ru2(2+)*2Cl(1-) In isopropanol at 82℃; for 0.166667h; Inert atmosphere; Stage #2: With potassium isopropoxide In isopropanol for 2h; Inert atmosphere; | |
99% | With LaCu0.67Si1.33; hydrogen In methanol at 120℃; for 10h; Autoclave; | |
99% | With C15H18BF3; hydrogen; phosphazene base P1-t-bu-tris(tetramethylene) In tetrahydrofuran at 75℃; for 20h; | |
98% | With dichloro-[1,3-bis(4-methylbenzyl)imidazolidin-2-ylidene](p-cymene)ruthenium(II); isopropanol; potassium hydroxide at 80℃; for 1h; | |
98% | With di-μ-chlorobis-[(η6-p-cymene)chlororuthenium(II)]; 1,3-bis(4-methylbenzyl)-3,4,5,6-tetrahydropyrimidinium chloride; isopropanol; potassium hydroxide at 80℃; for 1h; Inert atmosphere; Schlenk technique; Green chemistry; | |
98% | With [(CH2(NC(C6H5)N(C4H9)CHC)2)RhI2((C6H5)2PC2H4P(C6H5)2)](1+)*I(1-)=[(CH2(NC(C6H5)N(C4H9)CHC)2)RhI2((CH2P(C6H5)2)2)]I; isopropanol; potassium hydroxide In lithium hydroxide monohydrate for 24h; Reflux; | |
98% | With C18H37BrNO4P2Re; potassium-t-butoxide; hydrogen In toluene at 120℃; for 20h; Glovebox; Autoclave; | |
98% | With (1-(3,5-dimethyl benzyl)-3-methyl-1,3-dihydro-2H-benzo[d]imidazol-2-ylidene)p-cymeneruthenium(II) chloride; potassium hydroxide In isopropanol for 4h; Reflux; Inert atmosphere; Schlenk technique; | |
97% | With borohydride-form of an anion exchange polystyrene-divinylbenzene resin In methanol at 30℃; for 18h; | |
97% | With formic acid; C25H26ClIrN2; anhydrous sodium formate In lithium hydroxide monohydrate at 80℃; for 12h; Inert atmosphere; Large scale; | |
97% | With lithium aluminium hydride In diethyl ether at -78℃; for 2.5h; | Reduction with LiAlH4 (inverse addition) (GP 8) General procedure: A solution of LiAlH4 in diethyl ether (1 M, 6 mL, 6 mmol) was added dropwise to the cooled (dry ice/acetone bath) solution of the respective carbonyl compound (20 mmol for ketones, 10 mmol for esters, 7.5 mmol for carboxylic acids) in diethyl ether (20 mL), and the mixture was stirred at -78 °C for an additional 30 min. The flask was immersed in an ice/water bath, the mixture was stirred for an additional 2 h, and a saturated aqueous NH4Cl solution was added dropwise under vigorous stirring (careful - foam) until the H2 gas evolution ceased. The mixture was stirred for an additional 15 min, filtered with suction through a pad of Celite, the filter cake was washed with diethyl ether (3 × 50 mL), and the combined filtrates were concentrated under reduced pressure to give the target alcohol. |
97% | With phenylsilane; C14H15MnN5O3(1+)*BF4(1-) In acetonitrile at 80℃; for 2h; | |
97% | With C28H25BrMnN2O3P; potassium-t-butoxide; hydrogen In tert-Amyl alcohol at 60℃; for 20h; Glovebox; Autoclave; | |
97% | With [(η6-C10H14)Ru(ampi)Cl]Cl; potassium hydroxide In isopropanol at 82℃; for 0.5h; | |
97% | With fac-[Mn((1,2-bis(di-isopropylphosphino)ethane))(CO)3(CH2CH2CH3)]; hydrogen In diethyl ether at 25℃; for 24h; Inert atmosphere; Glovebox; Autoclave; | |
97% | With hantzsch ester; lithium hydroxide monohydrate; sodium hydroxide In isopropanol; acetonitrile for 30h; Inert atmosphere; Irradiation; | 3 Example 3 The hydrogen transfer reaction of 4-fluoroacetophenone catalyzed by a nitrogen-containing heterocyclic thiol monovalent copper compound Add 1mmoL4-fluoroacetophenone, 0.1mmoLNaOH, 0.3mmoLHEH and 4mg of nitrogen-containing heterocyclic mercaptan monovalent copper compound into a dry reflux reaction tube with a magnetic stirrer, and then add 5mL, volume ratio of 3:1 The mixed solution of water isopropanol and acetonitrile is stirred for reaction. During the reaction, replace with neon gas 3 times, use blue LEDs as the light source of catalytic reaction, stir the reaction for 30h, add 5mL water after completion, extract with 3×5mL ethyl acetate, combine the organic phases, and dry with anhydrous magnesium sulfate After filtering, the filtrate is concentrated by rotary evaporation, and the target product is obtained by silica gel column chromatography. The yield of the target product is 97%. |
96% | With Cp2Ti(BH4) In 1,2-dimethoxyethane for 6h; | |
96% | With dichloro-[1-(2,3,4,5,6-pentamethylbenzyl)-3-(2-methoxyethyl)benzimidazol-2-ylidene]ruthenium (II); isopropanol; potassium hydroxide at 80℃; for 1h; Inert atmosphere; | |
96% | With dicarbonyl-(η4-3,4-bis(4-methoxyphenyl)-2,5-diphenylcyclopenta-2,4-dienone)(1,3-dimethyl-4-phenyl-1,2,3-triazolylidene)ruthenium In isopropanol for 8h; Reflux; | General conditions for transfer hydrogenation Complex 3a (12mg, 15μmol, 5mol%), CAN (8mg, 15μmol, 5mol%) and iPrOH (5mL) were stirred at reflux for 15min. Then 4-fluoroacetophenone (36μL, 300μmol) was added and samples were taken at regular intervals. Aliquots (ca. 0.05mL) were diluted with CDCl3 (0.5mL) and conversions were determined by 1H NMR spectroscopy. |
96% | With ethanol; (dcype)Ni(COD) In neat (no solvent) at 130℃; for 36h; | |
96% | With [Re(NH{CH2CH2P(iPr2)}2)(CO)3]Br; potassium-t-butoxide; hydrogen In toluene at 70℃; for 17h; Inert atmosphere; Glovebox; Autoclave; | |
96% | With [(bromo)(hydrido)(carbonyl)(1R)-N2-(3,5-dihydro-4H-dinaphtho[2,1-c:1',2'-e]phosphepin-4-yl)-N6-((diisopropylphosphanyl)pyridine-2,6-diamine)iron(II)]; potassium-t-butoxide; hydrogen In ethanol at 20℃; for 18h; | |
96% | With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H2O); isopropanol In lithium hydroxide monohydrate at 82℃; for 6h; Inert atmosphere; Schlenk technique; chemoselective reaction; | |
96% | With Mn(CO)<SUB>3</SUB>Br(k<SUP>2</SUP>P,N-Ph<SUB>2</SUB>PN(H)Py); hydrogen; 1,1,1,3,3,3-hexamethyldisilazane potassium In toluene at 50℃; for 20h; Glovebox; Autoclave; Inert atmosphere; | |
96% | With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H2O); isopropanol at 82℃; for 6h; Inert atmosphere; Green chemistry; | 6 1-(4-Fluorophenyl)ethanol The 4 - fluoro acetophenone (138 mg, 1.0 mmol), cat. [Ir] (1.1 mg, 0 . 002 mmol, 0.2 μM %) and isopropyl alcohol (5 ml) are added to the 25 ml Kjeldahl tube, N2Protection Cooling to room temperature, rotary evaporation to remove the solvent, then through the column chromatography (developing solvent: petroleum ether/ethyl acetate) to obtain the pure target compound, yield: 96% |
96% | With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H2O); hydrogen In tert-Amyl alcohol at 30℃; for 12h; Green chemistry; | 4.2. General procedure for catalytic hydrogenation of 2 General procedure: To an oven-dried 5 mL round-bottom flask were added ketone (1 mmol), cat. 7 (2.7 mg, 0.5 mol %) and tert-amyl alcohol (1 mL). Next, vacuum was applied to the flask followed by filling with H2 gas and keeping the flask attached to a balloon filled with H2 gas. The mixture was heated at 30 °C for 12 h. After completion of the reaction, the solvent was removed by evaporation under reduced pressure. The alcohols were isolated and purified by filtering a hexanes/ethyl acetate (5:1) solution of the crude product through a pad of silica gel, and then removing the solvent under reduced pressure. The conversion and purity of the alcohol products was assessed using NMR spectroscopy. |
96% | 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. |
96% | With C37H43MoN3O2P; sodium triethylborohydride; isopropanol; sodium hydroxide In tetrahydrofuran at 90℃; for 4h; Schlenk technique; Inert atmosphere; | 13.2 General procedure: Add 2.5mmol aromatic ketone, 10-20mg (2.5-5.0mmol, 1-2eq.) NaOH, 10μmmol (0.4mol%) Mo-8, 0.1mL (0.1mmol) NaBHEt3(1M in THF) in the schlenk bottle in sequence , 5mL dry isopropanol, use a double-row tube to remove the air in the system, and fill it with nitrogen. The reaction was stirred at 90°C (oil bath temperature) for 2 to 5 hours, the reaction system was cooled, and the conversion rate of aromatic ketones and the yield of reducing alcohol were shown in Table 4 by GC detection and analysis (dodecane was the internal standard). |
95% | With sodium tetrahydridoborate In methanol at 0℃; for 1.5h; | |
95% | With [IrH(1,5-cyclooctadiene)Cl(HCN(i-Pr)CHCN(C2H4PPh2))]PF6; isopropanol; potassium hydroxide for 4h; Inert atmosphere; | General procedure for Transfer Hydrogenation of Acetophenones and enones General procedure: To a 10 mL Schlenk tube equipped with a stir bar was charged with ketone (1 mmol), KOH (0.05 mmol), and iPrOH (3 mL). The mixture was degassed by bubbling N2, and 0.1 mol % of catalyst 2 for entry 1-10 and 0.5 mol% of 2 for entry 11-19, was added under a steady flow of N2. After removal any inorganic salts by filtration, all the volatiles were removed under reduced pressure. The pure product could be obtained by silica gel chromatography (ethyl acetate/hexane). The identity of these products have been confirmed by comparisons of the obtained spectra with those previously reported. |
95% | With cis-[(H)(SePh)Fe(PMe3)4]; sodium tertiary butoxide In isopropanol at 80℃; for 24h; | |
95% | With C28H35ClCoN5(1+)*Cl(1-); potassium-t-butoxide; hydrogen In tetrahydrofuran at 20℃; for 16h; Autoclave; | General procedure for Hydrogenation of Ketones General procedure: In an argon filled glove box, the cobalt catalyst (LNHC/CoCl2 or Co-2a) and the base wereweighted into a 4mL vial equipped with a magnetic stir bar, followed by addition of the solvent.After shaking of the vial for 30 seconds, the carbonyl substrate was then added. The vial wasplaced into a Parr Instruments autoclave, which was then sealed, removed from the glove boxand purged with hydrogen gas. The autoclave was heated to certain temperature. After reactionfor 16 hours, the autoclave was cooled down to 0 oC before releasing the hydrogen gas. Forquantitative GC analysis, biphenyl (1.0 mmol) as internal standard was added. The organiclayer was then filtrated and diluted for GC analysis. The stereo-selectivity of the hydrogenatedproducts of cyclohexanones were determined by NMR with mesitylene as the internal standard.The desired hydrogenation product was further isolated by flash column chromatography. |
95% | With methanol; sodium tetrahydridoborate at 0 - 20℃; for 1h; | 1.1 Step 1: Preparation of l-(4-fluorophenyl)ethan-l-ol (2) To the stirred solution of l-(4-fluorophenyl)ethan-l-one (1, 2.0 g, 17.6 mmol) in MeOH (20 mL), was added NaBH4(1.0 g, 26.5 mmol) portion wise at 0 °C and stirred at rt for 1 h (Reaction condition a). The reaction mixture was quenched with ice and the MeOH was evaporated. To the resulting crude added water (10 mL) and extracted with EtOAc (2 X 25 mL). Organic layer was washed with brine (10 mL) solution, dried over anhydrous Na2S04and evaporated under vacuum to give the product as colourless oil (2) (1.9 g, 95%, Yield).XHNMR (400 MHz, DMSO-d6) δ (ppm): 7.36-7.33 (m, 2H), 7.14-7.07 (m, 2H), 5.12 (d, = 4.0 Hz, 1H), 4.72-4.67 (m, 1H), 1.28 (d, = 6.8 Hz, 3H). |
94% | Stage #1: 1-(4-Fluorophenyl)ethanone With Triethoxysilane; diethylzinc(II); N,N-dimethyl-N'-(4-tert-butylphenyl)formamidine In tetrahydrofuran; hexane at 20 - 60℃; Inert atmosphere; Stage #2: With sodium hydroxide In tetrahydrofuran; hexane; lithium hydroxide monohydrate at 0℃; for 1h; | |
94% | With mesoporous silica; 4,4,5,5-tetramethyl-1,3,2-dioxaborolane; sodium tertiary butoxide In toluene at 22℃; for 2.5h; Inert atmosphere; | |
94% | With C16H33Cl2CoN5P2; hydrogen; sodium tertiary butoxide In tert-Amyl alcohol at 20℃; for 24h; Autoclave; | |
94% | With [Cu(bathocuproine)(Xantphos)]PF6; [Co(trifluoromethanesulfonate)(1,4-di(picolyl)-7-(p-toluenesulfonyl)-1,4,7-triazacyclononane)](trifluoromethanesulfonate); lithium hydroxide monohydrate; triethylamine In acetonitrile at 30℃; for 5h; Irradiation; Inert atmosphere; | |
94% | With formic acid; C18H24ClIrN3 In lithium hydroxide monohydrate at 80℃; for 4h; Schlenk technique; Inert atmosphere; chemoselective reaction; | |
93% | With dichloro(p-cymene)ruthenium(II) dimer; dimethylamine borane In tetrahydrofuran at 70℃; for 24h; Inert atmosphere; Sealed ampoule; | Representative procedure for metal-catalysed transfer hydrogenation General procedure: To an oven dried, argon purged, ampoule containing [Ru(p-cymene)Cl2]2 (15.3 mg, 0.05 mmol, 2.5 mol%), substrate (1 mmol) and dry thf (to make a total of 3 mL), a solution of dimethylamine borane in thf was added. The ampoule was sealed and heated at 70 °C for 24 hours then cooled to room temperature; Method A - The reaction mixture was diluted with CH2Cl2 (30 mL) and passed through a short pad of silica followed by diethyl ether (100 mL). The solvents were concentrated in vacuo to afford the crude product. |
93% | With trimethylamine-N-oxide; (N,N,N-trimethyl-2-(5-oxo-4,6-bis(trimethylsilyl)cyclopenta[c]pyrrol-2-(1H,3H,5H)-yl)ethanaminium) iron tricarbonyl; hydrogen In lithium hydroxide monohydrate at 85℃; for 14h; Autoclave; Inert atmosphere; | |
93% | With CdS(x)Se(1-x) x:0-1;; caesium acetate; para-thiocresol In toluene for 8.5h; Sealed tube; Inert atmosphere; Irradiation; | |
93% | With [Cp*Ir(2,2'-bpyO)(OH)][Na]; hydrogen In lithium hydroxide monohydrate at 30℃; for 12h; | 9 The method is: 4-Fluoroacetophenone (138 mg, 1.0 mmol), metal ruthenium complex [Cp*Ir(2,2'-bpyO)(OH)][Na] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) are added to 25 ml round bottom flasks, and the air in the round bottom flask is replaced with hydrogen. The pressure of hydrogen gas in the system during the entire process of the reaction was 1 standard atmospheric pressure, and the reaction mixture was reacted at 30 °C, the hydrogen atmosphere was 12 h. After the reaction is completed, the solvent is removed by the column chromatography (eluent: petroleum ether / ethyl acetate volume ratio = 8: 1), yield: 93%. |
92% | With sodium tetrahydridoborate In isopropanol for 3.5h; Ambient temperature; | |
92% | Stage #1: 1-(4-Fluorophenyl)ethanone With n-butyllithium; ferrous acetate; 1,3-bis(2,6-diisopropylphenyl)imidazolinium chloride In tetrahydrofuran; hexane at 65℃; Inert atmosphere; Stage #2: With sodium hydroxide In tetrahydrofuran; methanol; hexane; lithium hydroxide monohydrate at 20℃; for 3h; Inert atmosphere; | |
92% | Stage #1: 1-(4-Fluorophenyl)ethanone 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; | |
92% | With C13H8BrMnN2O5; potassium-t-butoxide In isopropanol at 80℃; for 24h; Inert atmosphere; Sealed tube; | |
91% | With RuCl2(p-cymene)(N-(2,3,5,6-tetramethylbenzyl)benzimidazole); potassium-t-butoxide In isopropanol at 80℃; for 12h; Inert atmosphere; Schlenk technique; | General procedure for the transfer hydrogenation of ketones General procedure: Under an inert atmosphere, a mixture containing the complexes [RuCl2(1-alkylimidazoline)(pcymene)]/[RuCl2(1-alkylbenzimidazole)(p-cymene)] (3a-f) (0.01mmol), KOBut (5 mmol%),ketone (1 mmol) was heated at 80 C in i-PrOH (10 mL) for 12 h. The solvent was removed under reduced pressure and product distribution was determined by 1H NMR spectroscopy and GC. |
91% | With C22H27BrN2ORu; isopropanol; potassium hydroxide for 1h; Reflux; Inert atmosphere; | |
90% | With C37H28Cl2N5PRu; isopropanol; sodium hydroxide at 82℃; for 0.0333333h; Inert atmosphere; | |
90% | Stage #1: 1-(4-Fluorophenyl)ethanone With Ru(HOC<SUB>5</SUB>H<SUB>3</SUB>NCH<SUB>2</SUB>C<SUB>5</SUB>H<SUB>3</SUB>NC<SUB>5</SUB>H<SUB>7</SUB>N<SUB>2</SUB>)(PPh<SUB>3</SUB>)Cl<SUB>2</SUB>; isopropanol at 82℃; for 0.166667h; Inert atmosphere; Stage #2: With potassium isopropoxide; isopropanol at 82℃; for 0.333333h; | |
90.1% | Stage #1: 1-(4-Fluorophenyl)ethanone With [N,N'-(1,2-dimethyl-1,2-ethanediylidene)bis[3-(diphenylphosphino)-1-propanamine]]Ni; phenylsilane In hexadeuterobenzene at 60℃; for 24h; Inert atmosphere; Glovebox; Stage #2: With lithium hydroxide monohydrate; sodium hydroxide In hexadeuterobenzene at 25℃; for 2h; | |
90% | With C18H37ClMoNO2P2; hydrogen; sodium triethylborohydride In tetrahydrofuran; toluene at 80 - 130℃; for 16h; Inert atmosphere; Autoclave; | |
90% | With methanol; [Cp*Ir(2,2'-bpyO)(OH)][Na] at 66℃; for 12h; Inert atmosphere; Schlenk technique; | |
89% | With C56H55ClN3P2Ru(1+)*F6P(1-); potassium 2-methyl-2-butoxide In isopropanol at 20 - 80℃; for 1.5h; Schlenk technique; Inert atmosphere; | |
89% | Stage #1: 1-(4-Fluorophenyl)ethanone With pyridine N-oxide; Triethoxysilane; C27H47FeP3Si In tetrahydrofuran at 50℃; for 6h; Schlenk technique; Stage #2: With sodium hydroxide In tetrahydrofuran; methanol at 60℃; for 24h; Schlenk technique; | |
89% | With (2-aminomethylpyridine); manganese(I) pentacarbonyl bromide; potassium-t-butoxide; hydrogen In tetrahydrofuran at 120℃; for 12h; Autoclave; chemoselective reaction; | 4.3. Representative procedure for the catalytic hydrogenation reactions General procedure: A 4 ml glass vial was sequentially charged with solid [Mn(CO)5Br](0.015 0.030 mmol), the substrate (0.5 mmol), 2-picolylamine(0.015 0.030 mmol), and a magnetic stirring bar. The reaction componentswere then dissolved in THF (2 ml) or 1,4-dioxane (2 ml)whereupon the resulting yellow solution was then gently stirred(200 rpm) for a period of 5 min. Whilst stirring, the glass vial was sealed with the septum cap. Hereafter, solid t-BuOK (0.015 0.030 mmol) was added to the reaction mixture upon which the reaction vessel was again sealed with a septum cap which was then penetrated with a needle.Notably, the base addition was carried out without stirring. After that,the glass vial was placed in a drilled aluminum liner which was promptly transferred into the 300 ml autoclave. Once tightly sealed, the latter was purged five times with H2 (20 bar per cycle) before being pressurized to the desired value. The autoclave was then placed on a pre-heated stirring plate and heated up to the required reaction temperature. On completion of the hydrogenation reaction, the autoclave was allowed to reach room temperature. Afterwards, the remaining gas was slowlyreleased upon which the reaction mixture was degassed through brieflystirring on air. Finally, n-dodecane (12 mg) or n-hexadecane (20 mg)were added and an aliquot of 30 μl was taken from the solution, mixedwith acetone (1 ml) whereupon the resulting solution was analyzed byGC. |
88% | With C34H28Cl2N3OPRu; potassium isopropoxide; isopropanol at 82℃; for 0.166667h; Inert atmosphere; Schlenk technique; | |
88% | With C12H19ClCoN5(1+)*Cl(1-); sodium tertiary butoxide In isopropanol at 85℃; for 24h; Inert atmosphere; | |
88% | With sodium tetrahydridoborate In ethanol at 20℃; Inert atmosphere; | |
87% | Stage #1: 1-(4-Fluorophenyl)ethanone With ferrous acetate; tricyclohexylphosphine In tetrahydrofuran at 65℃; Inert atmosphere; Stage #2: In tetrahydrofuran at 65℃; Inert atmosphere; Stage #3: With lithium hydroxide monohydrate; sodium hydroxide In tetrahydrofuran; methanol at 0 - 20℃; Inert atmosphere; | |
85% | With hydrogen at 80℃; | |
85% | With C9H8BrMnN2O3; potassium-t-butoxide In isopropanol at 80℃; for 0.333333h; Inert atmosphere; Schlenk technique; Glovebox; | |
85% | With methanol; sodium tetrahydridoborate at 0 - 20℃; for 0.666667h; Inert atmosphere; | |
84% | Stage #1: 1-(4-Fluorophenyl)ethanone With C40H32Cl2N3PRu; isopropanol at 82℃; for 0.166667h; Schlenk technique; Inert atmosphere; Stage #2: With sodium hydroxide for 1.5h; Schlenk technique; Inert atmosphere; | |
84% | With methanol; sodium tetrahydridoborate at 0℃; | |
83% | Stage #1: 1-(4-Fluorophenyl)ethanone With Cp(CO)2Mn(IMes); diphenylsilane In toluene at 25℃; for 1h; Schlenk technique; Inert atmosphere; UV-irradiation; Stage #2: With sodium hydroxide In methanol; toluene at 20℃; for 2h; Schlenk technique; Inert atmosphere; | |
83% | With methanol; sodium tetrahydridoborate at 20℃; for 24h; Microwave irradiation; Sealed tube; | |
83% | With C15H20ClN3NiO2; isopropanol; potassium hydroxide at 100℃; for 12h; Inert atmosphere; Glovebox; | |
82% | Stage #1: 1-(4-Fluorophenyl)ethanone With [CpFe(IMes)(CO)2]I; phenylsilane In toluene at 70℃; for 16h; Inert atmosphere; Irradiation; Stage #2: With methanol; sodium hydroxide In lithium hydroxide monohydrate; toluene at 20℃; for 1h; Inert atmosphere; | |
82% | Stage #1: 1-(4-Fluorophenyl)ethanone With Triethoxysilane; [cis-Fe(H)(SPh)(PMe3)4] In tetrahydrofuran at 60℃; for 24h; Stage #2: With methanol; sodium hydroxide In tetrahydrofuran; lithium hydroxide monohydrate at 60℃; for 24h; | 2.2. General procedure for catalytic hydrosilylation of aldehydes General procedure: To a 25 mL Schlenk tube containing a solution of 1 in 2 mL of THF was added an aldehyde (1.0 mmol) and (EtO)3 SiH (0.20 g, 1.2 mmol). The reaction mixture was stirred at 50-55 °C until there was no aldehyde left (monitored by TLC and GC-MS). The reaction was then quenched byMeOH (2mL) and a 10% aqueous solution of NaOH (5 mL) with vigorous stirring at 60 °C for about 24 h.The organic product was extracted with diethyl ether (10 mL × 3), dried over anhydrous MgSO4, and concentrated under vacuum. The alcohol product was further purified using flash column chromatography (elute with 5-10% ethyl acetate in petroleum ether). The 1H NMR and 13C NMR spectra of the alcohol products are providedin Supporting information. |
81% | With dichloro[1-(N-propylphthalimide)-3-(2,3,5,6-tetramethylbenzyl)imidazolidin-2-ylidene](p-cymene)ruthenium(II); isopropanol; potassium hydroxide for 1h; Inert atmosphere; Schlenk technique; Reflux; Green chemistry; | 2.13 General Method for the Transfer Hydrogenationof Ketones General procedure: The catalytic hydrogen transfer reactions were carried outin a closed Schlenk flask under argon atmosphere. Substrateketone (1 mmol), catalyst Ru(II)-NHC complex 3a-f (0.01 mmol) and KOH (4 mmol) was heated to reflux in10 mL of i-PrOH for 1 h. The solvent was then removedunder vacuum. At the conclusion of the reaction, themixture was cooled, extracted with ethyl acetate/hexane(1:5), filtered through a pad of silicagel with copiouswashings, concentrated, and purified by flash chromatographyon silicagel. The product distribution was determinedby 1H NMR spectroscopy, GC and GC-MS. |
80.2% | With isopropanol; potassium hydroxide at 69.84℃; for 14h; Green chemistry; | |
80% | With C17H13BrMnN3O3; sodium isopropanolate; isopropanol at 90℃; for 2h; Inert atmosphere; Sealed tube; | |
80% | With C16H9BrMnN3O4; potassium-t-butoxide In isopropanol at 85℃; for 24h; Inert atmosphere; Schlenk technique; | |
80% | With [{(pentamethylcyclopentadienylRh(2-phenylpyridnate)(μ-dppm)Pd(2-chlorophenyl thiosemicarbazone))}PF6]; sodium tertiary butoxide In ethanol at 90℃; for 8h; Sealed tube; | |
79% | With C15H13MnN3O3(1+)*Br(1-); potassium-t-butoxide; isopropanol at 70℃; for 24h; Schlenk technique; Inert atmosphere; | |
78% | With Triethoxysilane; C43H48FeP4 In tetrahydrofuran at 50℃; for 16h; | |
76% | Stage #1: 1-(4-Fluorophenyl)ethanone With Triethoxysilane; C23H30CoNP2 In tetrahydrofuran at 60℃; for 24h; Schlenk technique; Stage #2: With sodium hydroxide In methanol at 60℃; for 24h; | |
75% | With Ru((CH3CH2O)3Si(CH2)3N(CH2PPh2)2)2Cl2; potassium-t-butoxide; isopropanol at 80℃; for 12h; Inert atmosphere; | |
75% | With pyridine; potassium-t-butoxide; isopropanol In toluene at 135℃; for 12h; Inert atmosphere; Schlenk technique; | |
73% | Stage #1: 1-(4-Fluorophenyl)ethanone With phenylsilane; potassium-t-butoxide In toluene at 20℃; for 0.5h; Inert atmosphere; Stage #2: With lithium hydroxide monohydrate; sodium hydroxide In toluene at 0 - 20℃; chemoselective reaction; | |
73% | With [Ni(1,3-dimesitylimidazol-2-ylidene)Clcyclopentadienyl]; sodium triethylborohydride; diphenylsilane In tetrahydrofuran at 25℃; for 17h; Inert atmosphere; Schlenk technique; | |
67% | Stage #1: 1-(4-Fluorophenyl)ethanone With diphenylsilane In toluene at 20℃; for 19h; Stage #2: With hydrogenchloride In propan-2-one Further stages.; | |
66% | With hydrazine hydrate monohydrate In tetrahydrofuran at 20℃; for 24h; Sealed tube; | |
65% | Stage #1: 1-(4-Fluorophenyl)ethanone With nickel(II) acetate tetrahydrate; tricyclohexylphosphine In tetrahydrofuran at 100℃; for 16h; Stage #2: With sodium hydroxide In methanol | |
64% | With sodium tetrahydridoborate In methanol at 0℃; for 0.5h; | |
61% | With C46H60Fe2N4SSi; hydrogen In toluene at 50℃; for 20h; Autoclave; | |
60% | With C33H41ClN2O2Ru; potassium-t-butoxide at 80℃; | |
51% | Stage #1: 1-(4-Fluorophenyl)ethanone With 2.6-dimethylphenol; Triethoxysilane; diethylzinc(II) In tetrahydrofuran; hexane at 60℃; for 1h; Inert atmosphere; Stage #2: With sodium hydroxide In tetrahydrofuran; methanol; hexane; lithium hydroxide monohydrate at 0℃; for 1h; | |
40% | With dichloro-[1,3-bis(4-tertbutylbenzyl)benzimidazol-2-ylidene](p-cymene)ruthenium(II); potassium hydroxide In isopropanol at 80℃; for 1h; | |
36% | With methanol; bis[dichlorido(η5-1,2,3,4,5-pentamethyl-cyclopentadienyl)iridium(III)]; 6,6′-dihydroxy-2,2′-bipyridine; potassium hydroxide at 60℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With thionyl chloride; In dichloromethane; at 0 - 20℃; for 1.0h; | To a stirred solution l-(4-fluorophenyl)ethan-l-ol (2, 0.5 g, 3.57 mmol) in DCM (5 mL), was added SOCl2(0.7 mL, 7.10 mmol) drop wise at 0 C and the reaction mixture was stirred at rt for 1 h (Reaction condition b). The reaction mixture was evaporated under vacuum and dried to afford the product as brown oil (3) (0.5 g, 89%, Yield).XHNMR (400 MHz, DMSO-d6) delta (ppm): 7.53-7.51 (m, 2H), 7.21-7.16 (m, 2H), 5.36-5.33 (m, 1H), 1.76 (d, = 6.8 Hz, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With phosphorus tribromide; In dichloromethane; at 4 - 20℃; for 4h; | 1-(4-fluorophenyl)ethanol (1 equiv., 25 g) was taken up in dichloromethane (150 mL), and PBr3 (0.7 equiv., 12 mL) was added dropwise at 4 C. over a period of 20 min. The reaction mixture was stirred for 4 h at room temperature, then added to iced water (200 g) and extracted with dichloromethane (3*100 mL). The combined organic phases were dried over sodium sulphate, concentrated by evaporation in vacuo, and the liquid product (1-bromoethyl)-4-fluorobenzene was obtained (30 g, 83% yield). |
21.3% | With phosphorus tribromide; In chloroform; at 70℃; for 72h; | A solution of 1-(4-fluorophenyl)ethanol (0.455 mL, 3.57 mmol) and phosphoms tribromide (0.673 mL, 7.13 mmol) in CHC13 (10 mL) was heated at 70 C for 3 d. The reaction mixture was quenched in ice water and diluted in ethyl acetate. The organic layer was separated and washed with water followed by brine, dried over anhydrous sodium sulfate and concentrated in vacuo to get the crudematerial. The cmde product was purified on a silica gel column with Hexanes/CH2C1(2/1) to afford 1-(1-bromoethyl)-4-fluorobenzene (154 mg, 0.758mo1, 21.3 %) as acolourless oil. ?H NMR (400 MHz, CHLOROFORM-d) oe 7.49 - 7.40 (m, 2H), 7.09 - 7.00(m, 2H), 5.23 (q, J=7.0 Hz, 1H), 2.06 (d, J=6.8 Hz, 3H). |
With hydrogen bromide; In water; at 0 - 20℃; for 3h; | 4-Fluoro-alpha-methylbenzyl alcohol (7 g, 6.3 ml, 50 mmol) was added to 50 mL 48% aqueous solution of HBr at 0 C. The solution was allowed to stir at room temperature three hoursat which time it was extracted with hexane. After drying and concentrated, 10 g of a colorless oil was obtained. M+H+(203). |
With trimethylsilyl bromide; In dichloromethane; at 20℃; for 48h;Inert atmosphere; | 10.1.1: 1-(1-Bromoethyl)-4-fluorobenzene 0.5 g of 1-(4-fluorophenyl)ethanol is dissolved in 20 cm3 of dichloromethane, under an inert atmosphere, at a temperature close to 20 C. 1.24 cm3 of pure bromo(trimethyl)silane are introduced in two lots to the reaction mixture. The latter is stirred at a temperature close to 20 C. for 48 h, then it is washed with a saturated aqueous solution of sodium chloride, dried over a phase separation cartridge and concentrated using a rotary evaporator under reduced pressure (5 kPa). The 700 mg of crude product obtained are purified by filtration through a silica pellet (eluent: 10% ethyl acetate/90% cyclohexane). After concentrating the fractions under reduced pressure, 439 mg of 1-(1-bromoethyl)-4-fluorobenzene are obtained in the form of a colorless thick oil. NMR: ppm: 1.98 (d, J=6.8 Hz, 3H) 5.53 (q, J=6.8 Hz, 1H) 7.19 (t, J=8.8 Hz, 2H) 7.56 (dd, J=8.8, 5.4 Hz, 2H) EI: [M]+ m/z=202; [M-Br]+ m/z=123 | |
With hydrogen bromide; In water; at 0 - 20℃; for 3h; | 4-Fluoro-alpha-methylbenzyl alcohol (7g, 6.3ml, 50mmol) was added to 50 mL 48 % aqueous solution of HBr at 0 0C. The solution was allowed to stir 3 h at RT, at which time it was extracted with hexane. After drying and concentration, 10 g of a colorless oil was obtained. M+H+(203). | |
With phosphorus tribromide; In dichloromethane; at 0 - 26℃; for 16h; | To a solution of 1 -(4-fluorophenyl)ethanol (500 mg, 0.0036 mol, commercial source: Apollo) in dichloromethane (5 mL) at 0 °C, PBr3 (0.5 mL, commercial source: TCI) was slowly added and the mixture stirred at 26 °C for 16 h. Upon completion, the reaction mixture was concentrated under reduced pressure. NaHCC>3 solution (70 mL) was added and extracted with ethyl acetate (3x30 mL). The organic layers were combined and washed with brine (50 mL), dried over Na2S04, filtered and concentrated to afford crude 1-(1-bromoethyl)-4-fluorobenzene (310 mg) as a brown liquid. It was used in the next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With potassium fluoride; C46H34I4O6; 1,1,1,3,3,3-hexamethyl-disilazane; In dichloromethane; at -30℃; | At -30C, racemic alcohol (1m) 1.0 mmol was dissolved in 5 ml dichloromethane, the compound of formula 2 (wherein, R is I and n is 2; and pharmaceutically acceptable salts) 0.2 mol% as a catalyst and the addition of 0.7 eq., of silylating agent formula (5) (in the formula, R4 is methyl)and 1 equivalent of potassium fluoride was added and stirred for 12 hours. The mixture was filtered then concentrated to recover potassium fluoride. The residue was purified by flash chromatography (acetone /hexane / triethylamine = 1: 5: 0.025) to give the chiral alcohol (2m, 47% yield 95% ee, (S)-form). |
47% | With C45H32I4O6; 1,1,1,3,3,3-hexamethyl-disilazane; In dichloromethane; at -30℃; for 2.0h; | Theracemic alcohol (1m) 1.0 mmol at -30 C as the catalyst was dissolved in 5 mldichloromethane (wherein, R I and n is 2; and pharmaceutically acceptable saltsthereof) compound of the formula (2) the addition of 0.2 mol% of potassium andfluoro fluoride with one equivalent silylating agent of formula 5 (wherein, R is methyl) was added to 0.7 eq., and then was stirred for 12 hours.The mixture was filtered then concentrated to recover the potassium fluorideto. The residue was purified by flash chromatography (acetone / hexane /triethylamine = 1: 5: 0.025) to give the chiral alcohol; to give the (2m, 47%yield 95% ee, (S) -form). |
46% | With vinyl acetate; triethylamine; In hexane; at 20℃; for 12.0h; | Dissolve <strong>[403-41-8]1-(4-fluorophenyl)ethanol</strong> (1.24 g, 8.85 mmol) in n-hexane (29.5 mL),CAL-B (195 mg), vinyl acetate (1.60 mL, 17.7 mmol) and triethylamine (0.0710 mL, 0.885 mmol) were added.The reaction mixture was stirred at room temperature for 12 hours. The mixture was filtered to remove impurities and reduced pressure to remove solvent. The mixture was purified by silica gel column chromatography (n-hexane / EtOAc = 8: 1, Rf = 0.25 (n-hexane / EtOAc = 4: 1)) and purified.(S)-1-(4-fluorophenyl)ethan-1-ol (574 mg, 46%) was obtained as a colorless oil (Formula 9) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With Di-n-butylmagnesium; 4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at 40℃; for 24h; regioselective reaction; | |
1: 14 % Spectr. 2: 52.5 % Spectr. | With sodium tetrahydridoborate; β‐cyclodextrin In water monomer at 20℃; for 65h; | |
1: 52 % Spectr. 2: 16 % Spectr. | With sodium tetrahydridoborate; β‐cyclodextrin In water monomer at 20℃; for 65h; |
With C18H33N2OPRu; hydrogen In isopropanol at 80℃; for 18h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 59% 2: 11% | Stage #1: para-fluorostyrene With 1-bromo-butane; sodium tetrahydroborate; Aliquat 336 at 20℃; for 16h; Stage #2: With sodium hydroxide; dihydrogen peroxide at 40℃; for 1h; | |
Stage #1: para-fluorostyrene In carbon disulfide at 20℃; for 5h; Stage #2: With sodium hydroxide; dihydrogen peroxide In methanol; carbon disulfide at 0 - 20℃; for 2h; Further stages. Title compound not separated from byproducts.; | ||
1: 71 %Spectr. 2: 6 %Spectr. | Stage #1: para-fluorostyrene With sodium tetrahydroborate; iodine; ethylene dibromide In 1,2-dimethoxyethane at 25℃; for 20h; Stage #2: With dihydrogen peroxide; sodium hydroxide In water at 0 - 25℃; for 0.333333h; Overall yield = 77 percent; | Typical procedure for hydroboration of alkenes with borane from NaBH4 and I2 using the PV method (Condition B) General procedure: Iodide (305 mg, 1.2 mmol) and a magnetic stirring bar were placed at the bottom of a test tube (15 mmf × 130 mm), to which 1,2-dibromoethane (0.5 mL) was added slowly to dissolve the iodide. FC-72 (2mL) was added slowly using a syringe. Subsequently, NaBH4 (84 mg, 2.2 mmol), a solution of 4-methylstyrene (1a) (240 mg, 2.0 mmol) in DME (5.0 mL) was added slowly in order, forming four layers. A rubber septum was fitted to the test tube, and a needle equipped with a balloon, which acted asa reservoir of borane gas during the reaction, was then pricked into the septum. The air in the test tube was removed by a syringe until the balloon was completely flattened. The test tube was stirred slowlyfor 20 h at 25 °C, taking care not to mix the layers. The reaction mixture was then cooled to 0 °C withice while stirring. An aqueous NaOH solution (1 M, 1.35 mL) was added slowly in ten portions.Verifying that organic layer was changed to basic condition using a pH test paper, H2O2 solution (30%,0.5 mL) was added slowly in two portion. After 20 min stirring, the organic layer was taken up with aglass pipette to a separating funnel, and washed with water and brine three times. The organic layer was dried over Na2SO4. After filtration, the solvent was evaporated. The residue was then purified by column chromatography on silica gel, eluting hexane/ethyl acetate (8:2) afforded 2-(p-tolyl)-1-ethanol (2a) (172mg, 63%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With potassium fluoride; C46H34I4O6; 1,1,1,3,3,3-hexamethyl-disilazane; In dichloromethane; at -30℃; | At -30C, racemic alcohol (1m) 1.0 mmol was dissolved in 5 ml dichloromethane, the compound of formula 1 (wherein, R is I and n is 2; and pharmaceutically acceptable salts) 0.2 mol% as a catalyst and the addition of 0.7 eq., of silylating agent formula (5) (in the formula, R4 is methyl)and potassium fluoride was added and stirred for 12 hours. The mixture was filtered then concentrated to recover potassium fluoride. The residue was purified by flash chromatography (acetone /hexane / triethylamine = 1: 5: 0.025) to give the chiral alcohol (2m, 49% yield 96% ee, (R)-form). |
49% | With C45H32I4O6; 1,1,1,3,3,3-hexamethyl-disilazane; In dichloromethane; at -30℃; for 2.0h; | The racemic alcohol (1m) 1.0 mmol at-30 C as the catalyst was dissolved in 5 ml dichloromethane (wherein, R I andn is 2; and pharmaceutically acceptable salts thereof) compound of the formula(1) was added to a 0.2 mol% of potassium and fluoro fluoride with oneequivalent silylating agent of formula 5 (wherein, R is methyl) wasadded to 0.7 eq., and then was stirred for 12 hours. The mixture was filteredthen concentrated to recover the potassium fluoride to. The residue waspurified by flash chromatography (acetone / hexane / triethylamine = 1: 5:0.025) to give the chiral alcohol; to give the (2m, 49% yield 96% ee, (R) -form). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With [(Ph4Cp-OH)Ru(CO)2]2 In benzene-d6 at 70℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With sulfuric acid; In nitromethane; at 101℃; for 0.08333330000000001h;Microwave irradiation; | General procedure: beta-Dicarbonyl compound (3.0 mmol) and alcohol (1.0 mmol) were combined in 2 mL of nitromethane, and H2SO4 (2.7 muL, 0.05 mmol) was added, and the resulting mixture was stirred under 101 oC with the microwave irradiation (650 W, 70%) for 5 min. Then Na2CO3 (10 mg) was added to the reaction mixture to quench the reaction and the solvent of the reaction mixture was removed under reduced pressure and the residue was passed through the flash column chromatography on silica gel to afford the product. |
97% | With silica bonded N-propylsulfamic acid; In nitromethane; at 100℃; for 0.25h; | General procedure: To a mixture of 1,3-dicarbonyl compound (2 mmol),alcohol or styrene derivatives (1 mmol), and 0.6 gSBNPSA, was added 2 cm3 nitromethane as solvent. Themixture was stirred under reflux conditions and the reactionwas followed by TLC. After completion, the mixture wasfiltered, and the remaining was washed with warm ethanolto separate catalyst and nitromethane was removed underreduced pressure. Then, the crude products were recrystallizedfrom mixture of dichloromethane and n-hexane.All the synthesized products were known and characterized by comparison of their spectral and physical data withthose reported in literature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With [Ru(salophen)OTf]; In neat (no solvent); at 100℃; for 5.0h; | General procedure: In a test tube, 1,3-dicarbonyl compound (1.5 mmol), alcohol or alkene (1.0 mmol) and catalyst (0.013 mmol) were mixed and stirred at 100 C for 5 h under solvent-free conditions. At the end of the reaction, Et2O (10 ml) was added and the catalyst was filtered. The pure product was isolated by chromatography on a silica gel plate (petroleum ether/ethylacatate = 9/1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE 12 2-(4-Fluoro-alpha-methylbenzyl)-5-(4-methylsulfonylphenyl)-6-(4-fluorophenyl)-3(2H)-pyridazinone The title compound was prepared according to the method of Example 7, substituting 4-fluoro-alpha-methyl benzyl bromide (synthesised from 4-fluoro-alpha-methyl benzyl alcohol) for benzyl bromide. M.p.=185-186° C. 1H NMR (300 MHz, CDCl3) 67 1.84 (d, J=7 Hz, 3H), 3.07 (s, 3H), 6.43 (q, J=7 Hz, 1H), 6.91-7.11 (m, 7H), 7.31 (d, J=9 Hz, 2H), 7.52 (m, 2H), 7.9 (d, J=9 Hz, 2H). MS (DCl/NH3) m/e 467 (M+H)+, 484 (M+NH4)+. Elemental Analysis: calculated for C25H20F2N2O3S: C, 64.36; H, 4.32; N, 6.00. Found: C, 64.38; H, 4.07; N, 5.93. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | Stage #1: 1-(4-Fluorophenyl)ethanol With sodium hydride In DMF (N,N-dimethyl-formamide) at 0 - 20℃; for 0.75h; Stage #2: 2,6 difluorobenzonitrile In DMF (N,N-dimethyl-formamide) at 0 - 20℃; for 2.33333h; | 101.1 Example 101; 5-[1-(4-fluorophenyl)-I-methyl-ethoxy]-quinazoline-2,4-diamine; [00301] Step 1; A solution of alpha-methyl-4-fluorobenzyl alcohol (0.7 ml; 5.5 mmol) in dimethylformamide was added to a cooled (0 °C) slurry of sodium hydride (220 mg; 5.5 mmol) in dimethylformamide under nitrogen atmosphere. The reaction mixture was slowly warmed to room temperature, and stirred for 45 minutes. In another vessel, a solution of 2,6-difluorobenzonitrile (765 mg, 5.5 mmol) in dimethylformamide was chilled to 0 °C, and activiated anion was added over 20 minutes. Mixture was then stirred 2 hours at room temperature. The reaction mixture was poured on crushed ice-water, stirred, filtered, washed with water and dried to afford 1.1 g of 2-fluoro-6-[I-(4-flurophenyl)-ethoxy]-benzonitrile (78 % yield). |
With sodium hydride In N,N-dimethyl-formamide at 0℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With triethylamine; In dichloromethane; at 20℃; | Step 1 1 -(4-Fluorophenyl)ethyl methanesulfonate A mixture of l-(4-fluorophenyl)ethanol (300 mg, 2.14 mmol, 1.0 eq), MsCI (293 mg, 2.57 mmol, 1.2 eq) and TEA (941 mg, 3.2 mmol, 1.5 eq) in DCM (5 mL) was stirred at room temperature overnight. TLC (PE/EA = 3/1) showed the starting material was consumed completely. The reaction was quenched with aqueous citric acid solution and then extracted with DCM (5 mL x 3). The organic phase was dried over Na2S04, filtered and concentrated to give l-(4-fluorophenyl)ethyl methanesulfonate (400 mg, yield 86%), which was used in next step without further purification. |
With triethylamine; In N,N-dimethyl-formamide; for 0.5h; | Example 1; 5-Chloro-2-{ri-(4-fluorophenyl)ethyllthio}-N-(5-methyl-lH-pyrazol-3-yl)pyrimidin-4-amineTo a solution of 5-chloro-4-[(5-methyl-lH-pyrazol-3-yl)amino]pyrimidine-2-thiol (Intermediate 7, 100 mg) in DMF (10 ml) was added Et3N (0.8 ml) and l-(4-fluorophenyl)ethyl methanesulfonate (420 mg, readily prepared from the reaction of l-(4-fluorophenyl)ethanol and methanesulphonyl chloride in DMF, in the presence OfEt3N, for 30 minutes and used without any further purification). The resulting mixture was heated to 800C for 2 hours. The solvent was evaporated and the residue was partitioned between H2O and DCM. The organic layer was washed with saturated NEUCl^ solution, H2O and brine. The organic extracts were dried and evaporation gave a colored residue. Purification using a Gilson column (5%->95% MeCN/H2O) afforded the title compound (17.6 mg) as a mixture of enantiomers. The title compound obtained via this method of purification may be in the form of the trifluoroacetic acid salt. 1H NMR delta 9.42 (s, IH), 8.37 (s, IH), 7.54 (m, 2H), 7.25 (m, 2H), 6.40 (s, IH), 4.82 (m, IH), 2.27 (s, 3H), 1.56 (d, 3H). LC-MS: 362 [M-H]+. | |
With triethylamine; In dichloromethane; at 0 - 26℃; for 16.0h; | To a solution of <strong>[403-41-8]1-(4-fluorophenyl)ethanol</strong> (200 mg, 0.0014 mol, commercial source: Aochem) in dichloromethane (4 mL), triethylamine (0.4 mL, 0.0029 mol, commercial source: Finar) and mesyl chloride (0.16 mL, 0.0021 mol, commercial source: Avra) were added at 0 C. The reaction mixture was stirred at 26 C for 16 h. Upon completion, dichloromethane (60 mL) and water (10 mL) were added. The organic layer was dried over anhydrous Na2S04, filtered and the filtrate was concentrated under reduced pressure to afford crude 1-(4-fluorophenyl)ethyl methanesulfonate (300 mg) as a pale tellow liquid that was used in the next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tributylphosphine; 1,1'-azodicarbonyl-dipiperidine; In tetrahydrofuran; at 50℃; | EXAMPLE 5; Step A:; A mixture of compound 55.1a (0.5 g, 2.15 mmol), 4-fluoro-alpha-methylbenzyl alcohol (0.36 g, 2.58 mmol, 1.2 eq), reagent 55.1a' (0.65 g, 2.58 mmol, 1.2 eq) and PBu3 (0.644 ml., 2.58 mmol, 1.2 eq) in THF (6.0 ml_) was stirred at 50 0C overnight. The mixture was then filtered through a short pad of celite and washed with EtOAc. Solvent was concentrated to give the crude product. The crude residue was purified by column chromatography eluting with EtOAc/Hexane to yield compound 55.1b (0.28 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
The mixture of 5a (11.0g, 48mmol) and 5b (5.6g, 40mmol) in THF (100ml) was stirring at O0C, PBU3 (20ml, 80mmol) was added dropwise to the mixture, the mixture was stirring at O0C for 0.5h before the addition of ADDP (2Og, 80mmol). The resultant mixture was kept stirring at O0C for 0.5h, the slowly warmed up to 800C, and kept stirring at 8O0C for 48h. The mixture was cooled to RT, the white precipitate was filtered off, the filtrate was concentrated and purified via ISCO (EtOAc- Hexane = 1 :6) to obtain 5c as a light orange liquid. (7.6g). MH+ 356/354 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
17.2% | With potassium tert-butylate; In tert-butyl alcohol; for 24.0h;Reflux; | To a magnetically stirred mixture of <strong>[155-10-2]4-amino-2-chloro-5-fluoropyrimidine</strong> (11.10 g, 75.2 mmol) in 1-(4-Fluorophenyl)ethanol (11.70 g, 82.8 mmol) was added a 1.0 M solution of KOtBu in tBuOH (82.8 mL, 82.8 mmol) in one portion, and the resulting tan mixture was heated to reflux and stirred for 24 h. The solvent was removed in vacuo and the resulting red-orange oil was purified by flash chromatography (SiO2, 0?10% MeOH/CH2Cl2) to give 5.5 g of red-orange oil. The oil was suspended in hexanes (100 mL) and stirred for 16 h. Water (100 mL) was added to the unchanged mixture, and the biphasic system was stirred vigorously for 1 h. The resulting cream colored solid was collected by vacuum filtration, washed with warm water (55 C., 2×100 mL), and dried under vacuum at 55 C. for 16 h to give 5-fluoro-2-[1-(4-fluorophenyl)ethoxy]pyrimidin-4-ylamine (3.30 g, 17.2% yield) as a white solid: mp 96-98 C.; 1H NMR (300 MHz, CDCl3) delta 7.84 (d, J=2.6 Hz, 1H), 7.42-7.38 (m, 2H), 7.03-6.97 (m, 2H), 5.99 (q, J=6.6 Hz, 1H), 5.09 (br s, 2H), 1.61 (d, J=6.6 Hz, 3H); MS (ESI) m/z 252 (M+H)+, m/z 250 (M-H)-. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With lipase Novozyme 435 In toluene at 40℃; for 24h; Resolution of racemate; Enzymatic reaction; optical yield given as %ee; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With potassium phosphate; at 155℃; under 750.075 Torr; for 48.0h;Inert atmosphere; Sealed tube; Green chemistry; | Under nitrogen atmosphere, to a 15-mL Pyrex glass screw-cap tube were added 1-phenylethanol (1a: 0.613 g, 5 mmol), benzyl alcohol (2a: 0.543 g, 5 mmol), K3PO4 (531 mg, 2.5 mmol), and Pt-Sn/gamma-Al2O3 (catalyst III: 147 mg, 0.075 mol % Pt). The resultant mixture was stirred in the sealed tube at 155 C for 48 h. After cooled to ambient temperature, the catalyst and base were removed by centrifugation and washed with Et2O (2×5 mL). The combined supernatant was condensed under reduced pressure and subject to purification by silica gel column chromatography (eluent: petroleum ether (60-90 C)/EtOAc = 20:1, v/v), affording product 3a as a white solid (1.018 g, 96%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With trimethylsilylazide; copper(II) bis(trifluoromethanesulfonate); In dichloromethane; at 30℃; for 0.333333h; | General procedure: To a stirred solution of alcohol 1 (1.0 mmol) and azidotrimethylsilane(TMSN3; 1.5 mmol) in CH2Cl2 (2.0 mL) was added Cu(OTf)2(5 mol%), and the reaction mixture was stirred at r.t. (ca. 30 C) for 20 min. On completion of the reaction as indicated by TLC, the reactionwas diluted with H2O and extracted with EtOAc. The organiclayers were dried with anhydrous Na2SO4, filtered, and evaporatedunder vacuum. The crude residue was purified by column chromatography(60-120 mesh silica gel, 1:9; EtOAc-hexane). |
64% | With bismuth(lll) trifluoromethanesulfonate; trimethylsilylazide; In dichloromethane; at 20℃; for 1.0h; | General procedure: Bi(OTf)3 (1.0 mol%) was added to a solution of the appropriate secbenzylalcohol (1.0 equiv) and TMSN3 (1.2 equiv) in CH2Cl2 (4.0mL/mmol) at r.t. When the reaction was complete (TLC), the solventwas removed and the crude material was purified by column chromatography. |
64% | With bismuth(lll) trifluoromethanesulfonate; trimethylsilylazide; In dichloromethane; at 20℃; for 1.0h; | General procedure: Bi(OTf)3 (1.0 mol%) was added to a solution of the appropriate secbenzylalcohol (1.0 equiv) and TMSN3 (1.2 equiv) in CH2Cl2 (4.0mL/mmol) at r.t. When the reaction was complete (TLC), the solventwas removed and the crude material was purified by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; ferrocenium(III) tetrafluoroborate; ethylbenzene dehydrogenase; In water; tert-butyl alcohol; at 30℃;Enzymatic reaction; | General procedure: 2.1. Sample preparation Ethylbenzene dehydrogenase was purified from ethylbenzene-grown A. aromaticum cells as previously described [11,23]. The enzyme assays were routinely conducted at an optimum pH of 7.5 at 30 C in 20 ml of 100 mM Tris/HCl containing 200 μM ferrocenium (III) tetrafluoroborate and ethylbenzene dehydrogenase (100-300 μl of app. 1 mg/ml protein solution). The reactions were initiated by adding 100 μl of a stock solution of the respective substrate in tert-butanol (a list of substrates, their purities and producers is available in the Supporting Information). After an overnight incubation, the reaction mixtures were extracted from the water phase by solid-phase extraction using either C18 Polar Plus (J.T. Baker from Avantor Performance Materials, US) or polystyrene/divinylbenzene (PS/DVB) copolymers solid phase extraction (SPE) columns (Strata-X from Phenomenex, US or the equivalent Chromabond HR-X from Macherey-Nagel, Germany), which were eluted with 0.5 ml of isopropanol. The only exception to the procedure was the 2-ethyl-1H-pyrrole reaction mixtures (22). Due to the high polarity of the product derived from this compound, we were unable to concentrate the sample and exchange the solvent by SPE. Therefore, the enzyme was precipitated by the addition of 50% methanol, and it was removed by centrifugation. The supernatant was directly analyzed by non-chiral reversed-phase (RP)-LC. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With methanol; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; trichloroisocyanuric acid In dichloromethane at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85%; 11%Spectr. | With chloro-trimethyl-silane; In neat (no solvent); at 20℃; for 3.5h;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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With C19H34N3O2P2Re; potassium <i>tert</i>-butylate In toluene at 140℃; for 8h; Inert atmosphere; Sealed tube; | |
84% | With [(N,N'-bis(diisopropylphosphino)-2,6-diaminopyridine)Mn(CO)2H]; potassium <i>tert</i>-butylate; potassium hydroxide In toluene at 140℃; for 24h; Inert atmosphere; Green chemistry; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With nickel(II) triflate; 1,3-bis(dicyclohexylphosphine)propane In tert-Amyl alcohol at 120℃; for 24h; Inert atmosphere; Glovebox; Schlenk technique; Molecular sieve; | |
90% | With nickel(II) triflate; 1,1,1,3',3',3'-hexafluoro-propanol; 1,3-bis(dicyclohexylphosphine)propane In tert-Amyl alcohol at 150℃; for 24h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; | 6 Example 6: Preparation of N '- (1- (4-fluorophenyl) ethyl) benzohydrazide Under a nitrogen atmosphere, a 10 mL Schlenk reaction tube was charged with Ni (OTf) 2 (2.9 mg, 0.008 mmol), 1,3-(Dicyclohexylphosphine) propane (4.4 mg, 0.010 mmol), a mixed solvent of tert-amyl alcohol and hexafluoroisopropanol (1.2 mL, volume ratio1: 1) and stirred for 10 minutes. Benzohydrazide (55 mg, 0.4 mmol), 1- (4-fluorophenyl) ethanol (112 mg, 0.8 mmol) and molecular sieves (100 mg). The reaction tube was sealed and heated in a 150 ° C oil bath for 24 hours. After the reaction is stopped, cold However, the reaction solution was directly added to a silica gel column and eluted with petroleum ether and ethyl acetate (3: 1 by volume) to obtain pure N '- (1- (4-fluoro- Phenyl) ethyl) benzohydrazide in 90% yield. |
73% | With t-butylnitrite; (1,4-dimethyl-5,7-diphenyl-1,2,3,4-tetrahydro-6H-cyclopenta[b]pyrazin-6-one)ruthenium tricarbonyl complex; sodium t-butanolate In <i>tert</i>-butyl alcohol at 130℃; for 24h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With carbonyl bis(hydrido)tris(triphenylphosphine)ruthenium(II); potassium carbonate; 1,2-bis-(diphenylphosphino)ethane In dimethyl sulfoxide; acetone at 130℃; for 24h; Microwave irradiation; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With carbonyl bis(hydrido)tris(triphenylphosphine)ruthenium(II); potassium carbonate; 1,2-bis-(diphenylphosphino)ethane In dimethyl sulfoxide; acetone at 130℃; for 24h; Microwave irradiation; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With carbonyl bis(hydrido)tris(triphenylphosphine)ruthenium(II); potassium carbonate; 1,2-bis-(diphenylphosphino)ethane In dimethyl sulfoxide; acetone at 130℃; for 24h; Microwave irradiation; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
> 90% | With lithium hydroxide monohydrate; oxygen; sodium hydroxide; In tert-butyl alcohol; at 70℃; for 12h; | Benzyl alcohol (1.0 mmol), 1-(4-fluorophenyl)ethanol (0.50 mmol), Co-N-CMK-3-800C (10 mg, 1.0 mol%), LiOH·H2O (42 mg, 1.0 mmol) was added to 0.5 mL of 2.0 mol/L NaOH (1.0 mmol) and0.5 mL of t-butanol mixed solution. The system was evacuated, passed through O2, repeated 3 times, and stirred at 70 C for 12 h. Cold to roomAfter the temperature, 10 mL of H 2 O was added to the reaction mixture, and ethyl acetate (15 mL × 3) was applied. The extracts were combined and dried over anhydrous Na2SO4.The product was isolated by rotary distillation, silica gel column chromatography (ethyl acetate / petroleum ether = 1/10, v / v).It was confirmed to be (E)-1-(4-fluorophenyl)-3-phenylprop-2-en-1-one; product yield was >90%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With [Ni(dmpymt)2]6; potassium hydroxide In toluene; <i>tert</i>-butyl alcohol at 70℃; for 36h; Schlenk technique; Inert atmosphere; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 140℃; 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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | 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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; In ethyl acetate; at 90℃; for 4h;Green chemistry; | General procedure: To a mixture of substituted alcohol 1 (1 mmol) and substituted nitrile 2 (1 mmol), T3P 50 wt% in ethyl acetate (50 mol%) was added and stirred at 90 C. After the reactant disappeared (monitored by TLC), the reaction mixture was cooled to room temperature, excess of water was added and extracted with ethyl acetate and combined organic layer was washed with brine, dried over Na2SO4 and concentrated under reduced pressure. The crude product was purified by recrystallization using DCM: pet ether (1:9) mixture to get pure compound 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H2O); Cs2CO3 In tert-Amyl alcohol at 125℃; for 12h; Schlenk technique; | 4.2. General procedure for the cross-coupling of secondary alcoholswith alkenyl primary alcohols catalyzed by [Cp*Ir(2,20-bpyO)(H2O)](cat. 10) (Tables 1-3). General procedure: To an oven-dried 25 mL Schlenk tube were added secondaryalcohol (1 mmol), alkenyl alcohol (1.2 mmol), catal (0.01 mmol,1 mol%), Cs2CO3 (98 mg, 0.3 mmol, 0.3 equiv) and tert-amyl alcohol(1 mL). The mixture of reaction was heated under 125 C in an oilbath for 12 h. The reaction mixture was cooled to ambient temperature,concentrated in vacuo and purified by flash column chromatographywith hexanes/ethyl acetate to afford thecorresponding product.1-phenylhexan-1-one (3aa) [16b]. Purified by flash columnchromatography on silica gel (ethyl acetate/hexanes = 1/100);88% yield (155 mg) |
Tags: 403-41-8 synthesis path| 403-41-8 SDS| 403-41-8 COA| 403-41-8 purity| 403-41-8 application| 403-41-8 NMR| 403-41-8 COA| 403-41-8 structure
[ 52085-92-4 ]
5-Fluoro-2,3-dihydro-1H-inden-1-ol
Similarity: 0.90
[ 52085-92-4 ]
5-Fluoro-2,3-dihydro-1H-inden-1-ol
Similarity: 0.90
[ 52085-92-4 ]
5-Fluoro-2,3-dihydro-1H-inden-1-ol
Similarity: 0.90
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