Name: 93-03-8|(3,4-Dimethoxyphenyl)methanol|97%
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[ 120-14-9 ]
[ 93-03-8 ]

Yield	Reaction Conditions	Operation in experiment
100%	With bis-tri-n-butylstannane; phenylboronic acid In dichloromethane at 20℃; for 21h;
100%	With sodium tetrahydridoborate In methanol at 20℃; for 1h;	Step-I (Preparation of benzyl alcohols) General procedure: benzaldehyde derivatives (1 mmol) in methanol (15 mL), sodium borohydride (2 mmol) and stirred at room temperature for 1 h. Usual work-up, quantitative yield.
100%	With sodium tetrahydridoborate In methanol at 0℃; Inert atmosphere;

99%	With sodium tetrahydridoborate In isopropanol for 0.166667h; Heating;
99%	With [Ir(2,2':6',2'’-terpyridine)(1,10-phenanthroline)Cl](PF₆)₂; anhydrous sodium formate In ethanol; water monomer at 100℃; for 0.75h; 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.
98%	With sodium tetrahydridoborate In methanol at 0℃;
98%	With methanol; sodium tetrahydridoborate at 0℃; for 0.333333h;	1 PREPARATION 1 (3,4-dimethoxyphenyl)methanol Based on Org. Biomol. Chem. 2010, 8, 539-545 [0026] 10 g (60.2 mmoles, 1 eq.) of 3,4-dimethoxybenzaldehyde are dissolved in 300 mL of methanol and the solution is cooled to 0° C. 2.73 g (72.2 mmoles, 1.2 eq.) of NaBH4 are added in portions and the reaction mixture is stirred for 20 minutes and then hydrolysed using 10 mL of 1M aqueous HCl solution until the medium is at neutral pH. The solvent is removed under reduced pressure and the residue is extracted using 3×50 mL of dichloromethane. The organic phases are combined, dried over MgSO4, filtered and concentrated under reduced pressure to yield 9.88 g of a clear oil. [0027] Yield=98%
98%	With hydrogen In methanol at 20℃; for 4.1h; chemoselective reaction;	Typical procedure for hydrogenation of 3,4,5-trimethoxybenzyl-aldehyde (1a) to3,4,5-trimethoxybenzyl alcohol General procedure: A mixture of 1a (196 mg, 1 mmol) and 1%Pd/Ni bimetallic catalyst9 (60 mg, 30 wt %) in MeOH (10 mL) was stirred underH2 at room temperature and atmospheric pressure (on an atmosphericpressure hydrogenation apparatus) until the absorption of hydrogen ceased(3.5 h). After the catalyst was removed off by a magnetic stirring bar, thesolution was evaporated in a vaporator to give the product 2a
98%	With sodium tetrahydridoborate In methanol at 0℃; for 6h;	Synthesis of (3,4-dimethoxybenzyl)triphenylphosphonium (5) To a solution of 3,4-dimethoxybenzaldehyde (16.6 g, 100 mmol) in MeOH (200 mL, 0.5 M) was added NaBH4 (4.5 g, 120 mmol) in batches at 0 oC. After stirring for 6 h, the mixture was quenched by the addition of water (100 mL). The solvent was evaporated in vacuo and the remaining water phase was extracted with CH2Cl2 (100 mL × 3). The combined organic phases were washed with water (100 mL), brine (100 mL), dried over anhydrous Na2SO4 and concentrated to afford 3,4-dimethoxybenzyl alcohol as a colorless liquid (16.5 g, 98%)
98.7%	Stage #1: 3,4-dimethoxy-benzaldehyde In methanol at 35℃; for 0.166667h; Stage #2: With hydrogen In methanol at 45℃; for 5h;	1-12; 1-2 Process for the preparation of resveratrol, comprising the steps of: (1) Material Blending: veratraldehyde, methanol and a palladium catalyst mixed titanium complex; Veratraldehyde feed ratio of methanol and 0.5kg/L; Veratraldehyde mass and a palladium-titanium complex catalyst ratio of 5: 1; Mixing process conditions comprising: a mixing speed of 300rpm / min, temperature 35 °C, time 10min; (2) air displacement: first replacing the air with nitrogen three times, the nitrogen was replaced with hydrogen twice; (3) reduction with hydrogen: Process conditions include a pressure 0.4MPa, temperature 45°C, mixing speed 300rpm/min, time 5h; (4) a hydrogen substitution: After hydrogen reduction, the first relief to 0.02MPa, after evacuation to -0.09MPa and then filled with nitrogen gas to 0.02MPa; (5) standing: After hydrogen substitution, the mixed material is stopped upon standing 2H; (6) sedimentation: The material is pressed into the settling tank, settling 2H; (7) solid-liquid separation: settling the material after the solid-liquid separation through the filter; (8) removal of the solvent: methanol to recover at atmospheric pressure, the autoclave when the temperature was raised to 110 °C, a small amount of methanol was removed under reduced pressure and vacuum to the solvent removal reactor temperature to 135 °C, a small amount of methanol was removed to give veratryl alcohol.
97%	With diisopropoxyaluminium trifluoroacetate In dichloromethane for 0.5h; Ambient temperature;
97%	With sodium tetrahydridoborate; sodium hydrogen sulphate In acetonitrile at 20℃; for 0.416667h;
97.4%	With nickel(II) oxide; isopropanol In neat (no solvent) at 150℃; for 2h; Sealed tube;
97%	With γ-Al₂O₃; isopropanol at 180℃; for 0.666667h; Microwave irradiation; Sealed tube;
96%	With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H₂O); isopropanol at 82℃; for 6h; Inert atmosphere; Schlenk technique; chemoselective reaction;
96%	With C₃₁H₃₃IrN₄O₅; isopropanol at 82℃; for 6h; Inert atmosphere;	7 Example 7: 3,4-Dimethoxybenzyl alcohol (3,4-Dimethoxyphenyl)methanol3,4-Dimethoxybenzaldehyde (166 mg, 1.0 mmol), cat. [Ir] (1.1 mg, 0.002 mmol,0.2 mol%) andIsopropanol (5 mL) was sequentially added to a 25 mL Kelvin tube, protected with N2, and reacted at 82 ° C for 6 h.Cool to room temperature, remove the solvent by rotary evaporation, and then obtain the pure target compound by column chromatography (developing solvent: petroleum ether / ethyl acetate).Rate: 96%
95.4%	With methanol; sodium tetrahydridoborate at 0℃; for 0.5h;	1 Synthesis of XZY-3-S29: Anhydrous methanol (8.0mL) dissolved the raw material veratraldehyde (400.0mg, 2.4mmol, 1.0eq),Sodium borohydride (273.4mg, 7.2mmol, 3.0eq) was slowly added at 0°C, and after stirring for 30min,The reaction was monitored by TLC thin layer chromatography, the stirring was stopped, and 1 mL of acetone was added to quench the sodium borohydride.Add diatomaceous earth to filter in a hole funnel and distill under reduced pressure to obtain 381.7 mg of oily liquid veratryl alcohol with a yield of 95.4%.
94%	With sodium tetrahydridoborate In methanol at 25℃; for 2h;
93%	With butyltriphenylphosphonium tetrahydroborate at 20℃; for 0.0166667h;
93%	With methanol; sodium tetrahydridoborate at 20℃; for 8h;
93%	With isopropanol at 110℃; for 7h; Autoclave;
92%	With Cocos nucifera juice at 20℃; for 15h; Inert atmosphere;
92.3%	With sodium tetrahydridoborate In methanol at -10℃;	General procedure for the reduction of benzaldehydes General procedure: All benzaldehydes were reduced using the method developed by Brown8was slightly modified in this synthesis. A solution of piperonal 7 (300.0 mg, 2.0mmol) in methanol (50 mL), sodium borohydride (176.0 mg, 4.65 mmol) wasadded in small portions and carefully. The reaction mixture was stirred at -10C for 2 h. After work-up as in the reduction of alcohols, the resulting residuewas recrystallized from hexane to give a tan solid identified as compound 22.
91%	With methanol; sodium tetrahydridoborate at 0 - 20℃; for 0.5h;
90%	With sodium tetrahydridoborate In benzene at 20 - 25℃; for 1h;
90%	With benzyltriphenylphosphonium tetraborate In methanol at 20℃; for 0.0166667h;
90%	With isopropanol at 120℃; for 4h;	2.4. Catalytic reaction General procedure: The MPV reaction of the biomass-derived compounds with 2-propanol was carried out in an oil-heated condition in a 15 ml Ace pressure tube (Synthware, Beijing). Typically, aldehydes (1.0 mmol), catalysts (0.1 g), and 2-propanol (10 mL) were added into the reactor, and then placed into the oil bath at stated temperature of 80-140 °C, followed bythe magnetic stirring for specific time at 600 rpm. After completion, the reaction tube was cooled to room temperature with cold water in a beaker. The reaction mixture was centrifuged and collected for analysis. Quantitative analysis of reactants and products on a standard sample using toluene as an internal standard on a GC (Shimadzu Nexis GC-2030) equipped with an HP-5 capillary column (30.0m×250mm×0.25 mm) and a flame ionization detector. Identification of products were observed using GC-MS (GCMS-QP2010 Ultra) equipped with HP-5MS capillary column (30.0m×250mm×0.25 mm).
88%	With sodium tetrahydridoborate In methanol at 10℃; for 1.5h; Inert atmosphere;	Synthesis of 3,4-dimethoxybenzyl alcohol 8 In a round-bottomed flask of 100 mL is introduced veratraldehyde 2 (1.68 g, 10.12 160mmol) in MeOH (20 mL) and placed under a nitrogen atmosphere. NaBH4 (459 mg, 12.13 161mmol, 1.20 equiv.) is then added and the reaction mixture mechanically stirred at room 162temperature. Completion was achieved in 1.5 h as indicated by TLC. After evaporation of 163MeOH, the residue was suspended in water and extracted with EtOAc (3x15 mL). The 164combined organic layers were dried over magnesium sulfate, evaporated and the product 165used without further purification. 166Yield: 88%
87%	With bis-tri-n-butylstannane; mesoporous silica In toluene at 80℃; for 3h;
87%	With sodium tetrahydridoborate; nickel (II) chloride In tetrahydrofuran at 20℃; for 0.0833333h;
84%	With ethanol; aluminium; sodium iodide for 8h; Electrolysis; refluxe;
84%	With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; 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.
83.7%	With titanium (lll) chloride In tetrahydrofuran; water monomer for 0.166667h;
83%	With potassium fluoride on basic alumina; paraformaldehyd for 0.1h; microwave irradiation;
83%	With sodium tetrahydridoborate; Montmorillonite K₁₀ In hexane at 20℃; for 1.25h;
81%	With cucumber juice at 30 - 35℃; for 72h; Inert atmosphere; Green chemistry;
77.16%	With diisobutylaluminium hydride In tetrahydrofuran; toluene at 20℃; for 2h; Inert atmosphere; Cooling with ice;
72%	With potassium hydroxide In isopropanol at 90℃; for 18h; Schlenk technique; Sealed tube;
60%	With copper (I) iodide; sodium methoxide In methanol; 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 18h; Inert atmosphere;	General procedure for reduction of aldehyde andnitro compounds: General procedure: To a solution of aldehyde/nitro compound (1 g) in dry DMF/xylene was added sodiummethoxide (10 equiv.) in methanol (5 ml). CuI (1 equiv.) was added whereverrequired. Reaction mixture was flushed by nitrogen, kept at 120oCfor appropriate time under nitrogen balloon andwater (100 ml) was added. It was extracted with ethyl acetate (3x75 ml) andcombined organic layer was dried over Na2SO4. Filtratewas concentrated under vacuum and the residue was further purified by columnchromatography in ethyl acetate/hexane as an eluent with appropriate polarityto get the product.
58%	With lithium tert-butylate In isopropanol at 20℃; for 36h; UV-irradiation; Inert atmosphere;
51%	With bis(tricyclohexylphosphine)benzylidene ruthenium (IV) dichloride; potassium hydroxide In 1,4-dioxane at 80℃; for 20h;
51%	With sodium methoxide In methanol; N,N-dimethyl-formamide at 120℃; for 15h; Inert atmosphere;	General procedure for reduction of aldehyde andnitro compounds: General procedure: To a solution of aldehyde/nitro compound (1 g) in dry DMF/xylene was added sodiummethoxide (10 equiv.) in methanol (5 ml). CuI (1 equiv.) was added whereverrequired. Reaction mixture was flushed by nitrogen, kept at 120oCfor appropriate time under nitrogen balloon andwater (100 ml) was added. It was extracted with ethyl acetate (3x75 ml) andcombined organic layer was dried over Na2SO4. Filtratewas concentrated under vacuum and the residue was further purified by columnchromatography in ethyl acetate/hexane as an eluent with appropriate polarityto get the product.
31%	With whole cell cultures of dichomitus albidofuscus at 24℃; for 96h; Darkness; Microbiological reaction;	2.5. general procedure for preparative biotransformation General procedure: The substrate (1 mmol) was added to submerged cultures of DAL on the 3rd culture day. The reaction mixture was incubated on an incubation shaker at 150 rmin 1 (deflection 25 mm) under exclusion of light at 24 °C for 4 days. 10 g of NaCl was added to media, and the mixture was stirred for 10 min at 800 rpm (magnetic stirrer). For extraction, 50 mL of Et2O was added, and the resulting mixture was stirred for 20 min at 800 rpm (magnetic stirrer), and centrifuged for 5 min at 3000 × g to separatethe organic layer. The extraction was repeated three times. The combined organic layers were washed with brine (1 × 30 mL) and water (1× 30 mL), dried over Na2SO4 and evaporated to dryness. The resulting reaction mixtures were analysed by GC/MS and NMR spectroscopy.Products were purified by column chromatography on silica gel (eluent(pentane/ether) changed gradually: 10/1, 7/3, 1/1) to isolate the majorcomponents. The respective fractions were combined, concentrated in vacuum, and the 1H and 13C NMR spectra of the residuals were compared with those of reference compounds. Every biotransformation was repeated three times to verify the reproducibility of the experiments. The detailed information about experimental data and yields is provided in the Electronic Supplementary Information.
29.4%	With phenylselenomagnesium bromide In tetrahydrofuran for 13h; Ambient temperature;
	With methanol; palladium⁽⁰⁾ Hydrogenation;
	With methanol; platinum Hydrogenation;
	With ethanol; platinum Hydrogenation;
	With potassium hydroxide at 20℃;
	With ethanol; nickel Hydrogenation;
	With lithium aluminium hydride In diethyl ether
	With paraformaldehyd
	With sodium tetrahydridoborate In methanol Yield given;
85 % Spectr.	With hydrogenchloride; sodium cyanotrihydridoborate In methanol for 24h;
	With potassium hydroxide; paraformaldehyd 1.) methanol, 65 deg C; 2.) water, 70 deg C, 40 min, reflux, 20 min; Yield given;
	With sodium tetrahydridoborate In methanol; dichloromethane for 1h;
	With sodium tetrahydridoborate In methanol
72 % Spectr.	With tris isopropylate aluminium; isopropanol; trifluoroacetic acid In benzene for 2h; Ambient temperature;
	With sodium tetrahydridoborate In isopropanol
	With sodium tetrahydridoborate In methanol Ambient temperature;
	With sodium tetrahydridoborate In methanol at 20℃;
	With potassium hydroxide; isopropanol at 82.85℃; for 6h;
	With hydrogen; magnesium In methanol at 20℃; for 0.333333h;
	With potassium hydroxide In isopropanol at 82.84℃;
	With sodium tetrahydridoborate In methanol at 0℃; Inert atmosphere;
	With potassium borohydrate In methanol at 20℃;
	With potassium borohydrate In methanol at 0 - 20℃;
	With sodium tetrahydridoborate In isopropanol at 20℃;
	With sodium tetrahydridoborate In methanol at 0℃; Inert atmosphere;
	With sodium tetrahydridoborate In dichloromethane at 20℃; for 0.5h;	General procedure for the preparation of 4-aminomethyl-3-(substituted benzyloxyimino)pyrrolidine dimesylates (8a-w) General procedure: To a solution of various benzaldehydes 4aew (10 mmol) dissolved in methanol (50 mL) was added sodium borohydride (20 mmol) at room temperature, and the mixturewas stirred at the same temperature for 30 min and concentrated under reduced pressure. The residue was diluted with methylene chloride (500 mL) and washed with water, and dried over anhydrous Na2SO4, and concentrated under reduced pressure to give the corresponding crude phenylmethanols 5a-w
	With sodium tetrahydridoborate In methanol at 0 - 20℃; for 1h;
	With sodium tetrahydridoborate In isopropanol for 4h;
	With sodium tetrahydridoborate In methanol Sealed tube;
	With sodium tetrahydridoborate In methanol
83 %Chromat.	With [Cp*Rh(2,2'-bipyridyl)Cl]Cl; proflavine; triethanolamine In water monomer; N,N-dimethyl-formamide at 20℃; for 25h; Inert atmosphere; Irradiation; chemoselective reaction;
0.96 g	With sodium tetrahydridoborate In methanol at 0 - 20℃; for 4h;	Typical Procedures for the Preparation of Compounds 6A'- G' and 7A'- H'. General procedure: To a solution of 3,4-dimethoxybenzaldehyde (1 g, 6 mmol) in methanol was added NaBH4 (0.27, 7.2 mmol) at 0 °C. The reaction mixture was stirred at room temperature for 4 h, quenched with 3% aqueous HCl solution, and evaporated to dryness. The residue was extracted with CH2Cl2 and the organic layer was dried with MgSO4. Evaporation of the dried organic layer yielded 0.96g (3,4-dimethoxyphenyl)methanol (6D0) as a white solid.
	With sodium tetrahydridoborate In methanol for 2h;
	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.
97 %Chromat.	With isopropanol at 120℃; for 2h;
89 %Chromat.	With isopropanol at 180℃; for 6h; Autoclave;
	With sodium tetrahydridoborate In methanol at 20℃; for 1h;	4 In a 100 mL round-bottomed flask, 4D (2 g, 12.0 mmol) was added and dissolved in methanol (30 mL). Sodium borohydride (454 mg, 12.0 mmol) was added in portions at room temperature. The reaction was continued for 1 h at room temperature and the reaction solution was concentrated to a small volume. ,Water and ethyl acetate were added and the layers were extracted. The organic phase was collected, dried over anhydrous sodium sulfate, and spin-dried to give 4E as a colorless oil. 4E was dissolved in diethyl ether (25 mL), and phosphorus tribromide (712 μL) was added dropwise at room temperature. 7.50 mmol), complete reaction, reaction at room temperature for 1 h.The reaction solution was placed in an ice bath, saturated sodium bicarbonate was added to quench the reaction, and the mixture was further extracted with ethyl acetate, dried over anhydrous sodium sulfate, and spin-dried to obtain white solid 4F (1.48 g, yield 53.4%).
96 %Chromat.	With isopropanol at 140℃; for 2h;
	With sodium tetrahydridoborate In methanol at 0℃;
	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
	With isopropanol at 160℃; for 4h; Autoclave; Inert atmosphere; Sealed tube;
	With sodium tetrahydridoborate In methanol at 0 - 20℃; for 2h;
	With sodium tetrahydridoborate In ethanol at 20℃; for 0.5h;	1.2 General procedure: To asolution of 1a (8.6 g, 0.038 mol) in EtOH (10 mL), NaBH4 (0.53 g,0.014 mol) was slowly added under ice bath. After stirred at roomtemperature for 30 min, 5% HCl was added to adjust pH to 7.Concentrated under vacuum, residue was extracted with DCM(10 mL×3), then organic layer was dried over anhydrous Na2SO4and concentrated to get white solid
99 %Chromat.	With trans-[Ru(6-(4-methoxyphenyl)-2-aminomethylpyridine)(CO)(PCy₃)(PPh₃)][BAr^f₄]; potassium carbonate; isopropanol at 82℃; for 0.5h; Inert atmosphere; Schlenk technique;
91.7 %Chromat.	With isopropanol at 80℃; for 3h; Autoclave;
	With methanol; sodium tetrahydridoborate In tetrahydrofuran at 100℃; for 4.5h;	1.2. General procedure for synthesis of compounds, 6e General procedure: Compound 6e was synthesized from 5e via reduction using sodium borohydride (NaBH4). A mixture of 5e (2.00 g, 10.2 mmol) and granular NaBH4 (1.1 equiv.) in THF (25 mL) was refluxed at 100 °C. Methanol (20 mL) was added dropwise in to the mixture over 30 min. The mixture was cooled down to room temperature after 4 h of reflux. The mixture was neutralized by a step-wise addition of 37% HCl. The reaction mixture was filtered, the filtrate was dissolved and extracted with ethyl acetate. Excess solvent was evaporated off to yield the desired compound, 6e as white solid (95% yield) without further purification. 1H NMR (500 MHz, DMSO-d6) δ, ppm: 6.91-6.87 (m, 2H),6.79 (d, J = 8.5 Hz, 1H), 5.06 (t, J = 6 Hz, 1H), 4.40 (d, J = 5.5 Hz,2H), 4.02-3.96 (m, 4H), 1.34-1.29 (m, 6H).
	Multi-step reaction with 2 steps 1: 0.55C₂₇H₄₃N₃Si₃V*0.45C₂₇H₄₄N₃Si₃V / diethyl ether / 2 h / 20 °C / Inert atmosphere; Glovebox; Schlenk technique 2: air / diethyl ether
	With C₄₇H₅₃ClCuN₅⁽¹⁺⁾*Cl^(1-); potassium hydroxide In isopropanol at 82℃;
77 %Chromat.	With zirconia; isopropanol at 110℃; for 9h; Autoclave;
96.7 %Chromat.	With C₆H₄B₂O₄^(4-)*Zr⁽⁴⁺⁾; isopropanol at 100℃; for 6h; Sealed tube;
	With sodium tetrahydridoborate In methanol at 20℃; for 0.5h;
	With sodium tetrahydridoborate In methanol

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2
[ 93-03-8 ]
[ 21852-32-4 ]

Yield	Reaction Conditions	Operation in experiment
100%	With phosphorus tribromide In diethyl ether
100%	With phosphorus tribromide In benzene at 20℃;	Step-II (Preparation of benzyl bromides) General procedure: benzyl alcohols (1 mmol) in dry benzene (15 mL) and phosphorus tribromides (0.5 mL) and stirred at room temperature to get respective benzyl bromides in quantitative yields, usual work-up.
95%	With phosphorus tribromide In diethyl ether 1.) ice-cooling, 1 h, 2.) 23 deg C, 1 h;

95%	With 1H-imidazole; iodine In dichloromethane at 20℃; for 0.25h;
95%	With phosphorus tribromide In diethyl ether at 0 - 20℃; for 5h; Inert atmosphere;
95%	With phosphorus tribromide In diethyl ether at 0 - 20℃; for 5h; Inert atmosphere;
94%	With carbon tetrabromide; triphenylphosphine In benzene at 0℃; for 2h;
92%	With phosphorus tribromide In benzene for 2h; 0 deg C -> room temp.;
92%	With phosphorous pentoxide; potassium bromide In acetonitrile at 20℃; for 0.416667h;	General procedure for the bromination of alcohols using KBr/P₂O₅ General procedure: To a mixture of alcohol (1 mmol) and KBr (1.5 mmol, 0.18 g) in acetonitrile (5 mL), P2O5 (1.5 mmol, 0.23 g) was added and the reaction was stirred at room temperature for the time specified in Table 3. After reaction completion (TLC or GC), the reaction mixture was filtered and the residue washed with ethyl acetate (3 × 8 mL). The combined organic layers were washed with water (10 mL) and dried over Na2SO4. The solvent was removed under reduced pressure to afford the corresponding product. If necessary, further purification was performed by column chromatography.
90%	With carbon tetrabromide; triphenylphosphine In benzene at 0℃; for 2h;
90%	With phosphorus tribromide In diethyl ether Cooling with acetone-dry ice;
88%	With phosphorus tribromide In water monomer; toluene	4-Bromomethyl-1.2-dimethoxybenzene 4-Bromomethyl-1.2-dimethoxybenzene A solution of phosphorus tribromide (0.35 cm3, 3.66 mmol) in dried toluene (5 cm3) was added dropwise to a solution of 3,4-dimethoxybenzyl alcohol (1.23 g, 7.34 mmol), in dried toluene (10 cm3) at 0° C. under nitrogen. After 15 minutes, the solution was stirred at room temperature for a further 2 hours, poured onto crushed ice/water (10 cm3) and extracted with toluene (320 cm3). The toluene extracts were combined and washed with water (40 cm3), sodium bicarbonate (40 cm3), water (40 cm3), dried (MgSO4), and evaporated under reduced pressure to give the bromide (1.49 g, 88%) as white needles, mp 34-37° C. νmax(NaCl)/cm-1 3002, 2958, 2936, 2835, 1605 (ArH), 1593 (ArH), 1519 (ArH), 1265, 1245, 1212, 1160, 1143; δH (400 MHz, CDCl3): 3.88 (6H, d, J=7.6 Hz, 2OMe), 4.50 (2H, s, CH2Br), 6.80-6.96 (3H, m, ArH); bromide unstable at room temperature, therefore, no CHN or MS recorded;
85%	With phosphorus tribromide
85%	With phosphorus tribromide In dichloromethane at 20℃; for 3h; Inert atmosphere;	3,4-Dimethoxybenzyl bromide (10) To 3,4-dimethoxybenzyl alcohol (1680 mg, 10.0 mmol) in 20ml CH2Cl2 was added PBr3 (4065mg, 15.0mmol) dropwise under N2. The mixture was stirred for 3 h atroom temperature. 40 ml distilled water was added to the reaction mixture to quench excess PBr3, then extracted with chloroform. The organic layer was washed with brine and dried over anhydrous Na2SO4. The solvent was removed in vacuo to afford (10) as a pale yellow oil that solidifies into a white solid on standing, 85%. 1H NMR (400 MHz, CDCl3): δ6.955 (dd, J = 2.10, 8.16 Hz, 1H), 6.915 (d, J = 207 Hz, 1H), 6.811 (d, J = 8.17 Hz, 1H), 4.505 (s, 2H), 3.899 (s, 3H), 3.881 (s, 3H).
83%	With phosphorus tribromide In diethyl ether at 0 - 23℃;
82%	With phosphorus tribromide In dichloromethane Ambient temperature;
82%	With phosphorus tribromide In dichloromethane at 20℃; for 4h; Schlenk technique;
82%	With carbon tetrabromide; triphenylphosphine In dichloromethane at 0℃; for 4h; Reflux;
80%	With phosphorus tribromide; triethylamine In Carbon tetrachloride for 2h; Ambient temperature;
80%	With phosphorus tribromide In dichloromethane at 0 - 20℃;
77%	With N-Bromosuccinimide; triphenylphosphine In dichloromethane for 1h; Ambient temperature;
65%	With phosphorus tribromide In dichloromethane at 20℃; Inert atmosphere; Molecular sieve;	I 4-(bromomethyl)-1,2-dimethoxybenzene To a flame dried flask cooled under argon was added (3,4-dimethoxyphenyl)methanol (0.169 grams, 1.0 mmol, 1.0M in dichloromethane, stored over 4 angstrom molecular sieves, purchased from Fisher Scientific). While stirring at room temperature a solution of phosphorous tribromide (1.4 mL, 1.0M in dichloromethane, purchased from Fisher Scientific) was added slowly. Once complete, the reaction was diluted with water and the organic layer removed. The aqueous layer was washed twice more with dichloromethane, and the organic material combined. The organic material was next washed with aqueous sodium bicarbonate (saturated), dried with sodium sulfate, filtered and concentrated. Purification was done using a Teledyne ISCO on a silica support using a hexanes ethyl acetate gradient. Yield 65%. 1H NMR δ 6.96 (dd, 1H), 6.92 (d, 1H), 6.82 (d, 1H), 4.52 (s, 2H), 3.91 (s, 3H), 3.89 (s, 3H).
61%	With phosphorus tribromide In diethyl ether at 0 - 20℃; for 12h; Inert atmosphere;
60%	With sodium bromide for 0.15h; Irradiation; microwave;
59%	With carbon tetrabromide; triphenylphosphine In tetrahydrofuran at 60℃; for 1h;	57.A A. 3,4-Dimethoxybenzyl Bromide To a solution of 3,4-dimethoxybenzyl alcohol (10 g,59.5 inmol) , carbon tetrabromide (22 g, 65.4 iranol) , and THF(250 mL) was added triphenylphosphine (17 g, 65.4 mmol) inTHF (75 mL) . The reaction was heated at 60 °C for 1 h andconcentrated to an oil. To the residue was added 1:1 .CH2Cl2:Et20 and the resulting solid was filtered. Thefiltrate was concentrated and chromatographed on florisilwith CH2Cl2 to give the title compound (8.05 g, 59%).ijSIMR (300 MHz, DMSO-dg): 8 3.79 (m, 3H), 3.80 (m, 3H) , 5,35(s, 2H), 7.04 (m, 3H).
53.4%	With phosphorus tribromide In diethyl ether at 20℃; for 1h;	4 In a 100 mL round-bottomed flask, 4D (2 g, 12.0 mmol) was added and dissolved in methanol (30 mL). Sodium borohydride (454 mg, 12.0 mmol) was added in portions at room temperature. The reaction was continued for 1 h at room temperature and the reaction solution was concentrated to a small volume. ,Water and ethyl acetate were added to separate the layers. The organic phase was collected, dried over anhydrous sodium sulfate, and spin-dried to give 4E as a colorless oil.The 4E was dissolved in diethyl ether (25 mL) and phosphorous tribromide (712 μL, 7.50 mmol) was added dropwise at room temperature. The addition was complete and the reaction was carried out at room temperature for 1 h.The reaction solution was placed in an ice bath, saturated sodium bicarbonate was added to quench the reaction, and the mixture was further extracted with ethyl acetate, dried over anhydrous sodium sulfate, and spin-dried to obtain white solid 4F (1.48 g, yield 53.4%).
	With hydrogen bromide; benzene at 10℃;
	With hydrogen bromide In benzene
	With phosphorus tribromide
	With phosphorus tribromide In diethyl ether for 3h; Ambient temperature; Yield given;
	With phosphorus tribromide In diethyl ether at 0 - 20℃; for 6h;
	With carbon tetrabromide; triphenylphosphine In dichloromethane for 2h; reflux;
	With phosphorus tribromide for 7h;
	With carbon tetrabromide; triphenylphosphine In chloroform at 20℃; for 1.5h;	14.A A l L round bottom flask equipped with N2 inlet was charged with CBr4 (5.48 g, 16.53 mmol, 1 equiv) and CHCl3 (30 mL). To the solution was added PPh3 (8.67 g, 33.06 mmol, 2 equiv) under nitrogen atmosphere at room temperature. After stirring for 30 min at the same temperature, 3,5-dimethoxybenzyl alcohol (2.78 g, 16.53 mmol) was added. The reaction mixture was stirred for 1 hour again at the same temperature. To the mixture was added hexane (600 mL). After stirring for 14 hours, sticky brownish yellow material was sticking on the surface of the flask. The supernatant was decanted and filtered through a glass filter. And then the solvent was removed from the filtrate under reduced pressure to give a crude benzyl bromide.
	With phosphorus tribromide In dichloromethane at 0 - 20℃; Inert atmosphere;
	With phosphorus tribromide In dichloromethane at 20℃;
	With bromine; triphenylphosphine In dichloromethane at 20℃; for 2.5h;	1 Preparation of 4-(3,4-dimethoxybenzyl)-6,7-dimethoxy-1-methylisoquinolin-3-ol hydrochloride 2 To a solution of triphenylphosphine (950 mg, 3.62 mmol) in dry CH2Cl2 (15 mL) at 0° C. in a 50 mL round-bottomed flask equipped with a magnetic stirrer is added bromine (150 μL, 2.93 mmol) and the solution is stirred at 0° C. for 15 min, after which 3,4-dimethoxybenzyl alcohol (0.50 mL, 3.42 mmol) is added. The reaction mixture is stirred at RT for 2.5 h then concentrated under vacuum. To a solution of the freshly prepared bromide in toluene (8 mL) in a 20 mL microwave vial equipped with a magnetic stirrer was added 6,7-dimethoxy-1-methylisoquinolin-3-ol CCH 18060 (495 mg, 2.26 mmol) at RT followed by a 2 N aq. KOH solution (1.70 mL, 3.40 mmol) and the mixture was stirred at 110° C. for 15 min under microwave irradiation. After cooling to RT, the mixture was diluted with H2O (10 mL) before extraction with CH2Cl2 (50 mL). The organic phase was isolated and washed with brine (10 mL), dried over Na2SO4, filtered and concentrated at 40° C. under vacuum. Purification by column chromatography (SiO2, eluent CH2Cl2:MeOH=100:0 to 95:4.5) gave 4-(3,4-dimethoxybenzyl)-6,7-dimethoxy-1-methylisoquinolin-3-ol as a yellow solid (286 mg, 34% yield). A portion of the free base (43 mg) was dissolved in MeOH (2 mL) in a 10 mL round-bottomed flask equipped with a magnetic stirrer before addition of a 0.15 M HCl solution in MeOH (2 mL). The reaction mixture was stirred for 5 min at RT and concentrated at 40° C. under vacuum. The solid was then washed with cold MeOH to afford, after drying, 4-(3,4-dimethoxybenzyl)-6,7-dimethoxy-1-methylisoquinolin-3-ol hydrochloride 2 as a yellow solid (22 mg, 47% yield). MW: 405.87; Yield: 16%; Yellow solid; Mp (° C.): 211.9 (dec.). Rf (free base): 0.2 (CH2Cl2:MeOH=95:4.5). 1H-NMR (CD3OD, δ): 3.01 (s, 3H, CH3), 3.80 (s, 3H, OCH3), 3.82 (s, 3H, OCH3), 3.96 (s, 3H, OCH3), 4.01 (s, 3H, OCH3), 4.27 (s, 2H, CH2), 6.74-6.81 (m, 3H, 3ArH), 7.08 (s, 1H, ArH), 7.13 (s, 1H, ArH). 13C-NMR (CD3OD, δ): 17.2, 30.6, 56.2, 56.3, 56.6, 56.8, 102.9, 104.6, 112.1, 112.3, 114.8, 119.1, 120.7, 131.4, 140.1, 148.4, 149.8, 150.8, 150.9, 157.9, (1C not observed). MS-ESI m/z (rel.int.): 370 ([MH]+, 100).
	With phosphorus tribromide In dichloromethane at 0℃; for 0.5h;	General procedure for the preparation of 4-aminomethyl-3-(substituted benzyloxyimino)pyrrolidine dimesylates (8a-w) General procedure: To a solution of phenylmethanols 5a-w (5 mmol) dissolved in methylene chloride (50 mL) in an ice-water bath was added phosphorus tribromide (5.5 mmol), and the mixture was stirred at the same temperature for 30 min. The mixture was washed with cool water, dried over anhydrous Na2SO4 and concentrated under reduced pressure to yield (bromomethyl)benzenes 6aew as offwhite solids or light yellow oils
	With phosphorus tribromide In dichloromethane at 0 - 5℃; for 0.75h;	General procedure: crude product 2a which was then dissolved in anhydrous methylene chloride (50 mL) and cooled to 0-5 ºC by ice bath. To this solution was added dropwise phosphorus tribromide (0.5 mL, 5 mmol) over a period of 15 min and stirred for 0.5 h at the same temperature, and then washed with saturated brine (3 Χ 15 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give crude compound 3a.
7 g	With phosphorus tribromide In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere;
	With pyridine; phosphorus tribromide In dichloromethane at 0 - 20℃; for 1h; Inert atmosphere;
	With phosphorus tribromide In dichloromethane at 0℃; for 2h;
	With phosphorus tribromide
	With phosphorus tribromide In dichloromethane at 0℃; for 0.5h;
	With phosphorus tribromide In dichloromethane at 0℃; for 1h; Inert atmosphere;
	With phosphorus tribromide In dichloromethane at 0℃; for 1h; Inert atmosphere;
	With phosphorus tribromide In dichloromethane at 0℃; for 0.5h;
	With phosphorus tribromide In dichloromethane at 0℃; for 8h; Inert atmosphere;	8-Iodo-9-(3,4-dimethoxy-benzyloxy)-3-[1.3]dioxolan-2,3,5a,10c-tetrahydro-1H,6H-5-oxaacephenanthrylene-10b-carbonitrile (11) Under an Ar atmosphere, to a solution of 3,4-dimethoxy-benzyl alcohol (272 mg, 1.62 mmol) in CH2Cl2 (8.1 mL) was added dropwise PBr3 (305 μL, 3.24 mmol) at 0 °C, and the mixture was stirred for 8 h. The reaction was quenched with H2O, and the aqueous phase was extracted with CHCl3. The combined organic layers were washed with brine, dried over MgSO4, filtered, and concentrated in vacuo. The resulting bromide was used without purification.
	With phosphorus tribromide In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere;	Benzo[1,3]dioxol-5-ylmethyl-triphenyl-phosphonium bromide (10). General procedure: To a solution of the piperonyl alcohol (8) (2.0 g, 13.15 mmol) in anhydrous CH2Cl2 (30 mL), cooled to 0 °C and stirred, under an argon atmosphere, freshly distilled PBr3 (3.7 mL, 39.45 mmol), was added dropwise. The resulting solution was kept under stirring at 0 °C for a further 20 minutes. After, the ice bath was removed, maintaining the stirring for a further 2 h. The system was cooled again to 0 °C and a saturated solution of NaHCO3 (75 mL) was slowly added. Extraction was carried out with ethyl ether (3x 70 mL). The combined organic phases were washed with brine, dried over anhydrous Na2SO4, and concentrated under reduced pressure to afford crude bromide (9). This bromide (used immediately after its preparation) was solubilized with anhydrous acetonitrile (30 mL), treated with triphenylphosphine (3.45 g, 13.15 mmol) and stirred overnight, under reflux. Acetonitrile was removed under reduced pressure and the residue was recrystallized from ethanol to provide (5.21 g) Wittig salt (10) in 83% overall yield.
	With phosphorus tribromide; triethylamine In dichloromethane at 0 - 15℃;
	With pyridine; phosphorus tribromide In dichloromethane at 0 - 20℃; for 4h;
	With carbon tetrabromide; triphenylphosphine In dichloromethane at 20℃; for 2.5h;	Synthesis of (3,4-dimethoxybenzyl)triphenylphosphonium (5) To 500 mL round bottom flask was added CH2Cl2 (200 mL), CBr4 (32.5 g, 98.0 mmol) and PPh3 (51.4 g, 196.0 mmol). The solution was stirred for 30 min at room temperature. The above 3,4-dimethoxybenzyl alcohol (16.5 g, 98.0 mmol) was added and the reaction mixture was stirred for another 2 h. Then, to the mixture was added hexane (4.0 L) and the solution was stirred overnight. After filtering through a glass filter, the solvent was removed in vacuo to give the crude product, which was used in the next step without further purification.
	With phosphorus tribromide In diethyl ether
	With phosphorus tribromide In dichloromethane at 0 - 20℃; for 1h;
	With phosphorus tribromide In diethyl ether at 0 - 20℃; for 2h;
	With phosphorus tribromide In dichloromethane at 0℃; for 0.25h;

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3
[ 93-03-8 ]
[ 120-14-9 ]

Yield	Reaction Conditions	Operation in experiment
100%	With polymer supported perruthenate reagent In dichloromethane
100%	With benzyltriphenylphosphonium peroxymonosulfate for 0.0833333h;
100%	With butyltriphenylphosphonium chlorochromate In acetonitrile for 0.5h; Heating;

100%	With aluminium chloride anhydrous; 1-butyl-4-aza-1-azoniabicyclo[2.2.2]octane chlorochromate In acetonitrile for 2h; Heating;
100%	With iodosylbenzene; Cl-CH₂-PS supported 5-amino-1,10-phenanthroline-Ru In acetonitrile at 60℃; for 1h;
100%	With 1,3,5,7-tetrakis[4-(diacetoxyiodo)phenyl]adamantane; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In dichloromethane at 20℃;
100%	With K<SUB>2</SUB>OsO<SUB>4</SUB>.2H<SUB>2</SUB>O; potassium carbonate; potassium hexacyanoferrate(III) In water monomer; acetonitrile at 60℃; for 0.5h; chemoselective reaction;
100%	With oxygen In 1,3,5-trimethyl-benzene at 60℃; for 0.5h;	8.6 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.
99%	With dihydrogen peroxide In benzene at 70℃; for 3h;
99%	With laccase; 2,2,6,6-tetramethyl-1-piperidinyloxy free radical; oxygen In water monomer at 20℃; for 24h;
99%	With dihydrogen peroxide In water monomer; acetonitrile at 25℃; for 0.583333h;
99%	With dihydrogen peroxide In water monomer at 20℃; for 0.416667h;
99%	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).
99%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen In aq. phosphate buffer; acetonitrile at 20℃; for 24h; Enzymatic reaction;
99%	With titanium(IV) dioxide; oxygen at 29.84℃; for 6h; Sealed tube; Irradiation;
99%	With tert.-butylhydroperoxide; oxygen In decane; toluene at 80℃; Schlenk technique;
98%	With 1-benzyl-1-aza-4-azoniabicyclo<2.2.2>octane periodate In acetonitrile for 0.5h; Heating;
98%	With 1-benzyl-4-aza-1-azoniabiyclo<2.2.2>octane peroxodisulfate In acetonitrile for 0.5h; Heating;
98%	With ammonium hydroxide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen In ethanol at 50℃; for 24h;	5 4.5. General procedure for the aerobic alcohol oxidation General procedure: Under an air atmosphere, a Schlenk tube was charged with MCM-41-bpy-CuI (40 mg, 0.025 mmol), alcohol (0.5 mmol), TEMPO (4 mg, 0.025 mmol), aqueous ammonia (0.5 mmol, 25e28%, w/w) and EtOH (1.0 mL). The mixture was stirred at 50 °C for 18-48 h. After completion of the reaction, the reaction mixture was cooled to room temperature, diluted with ethyl acetate (10 mL), and filtered. The MCM-41-bpy-CuI complex was washed with EtOH (2*5 mL), and Et2O (5 mL) and reused in the next run. The filtrate was concentrated under reduced pressure and the residue was purified by flash column chromatography on silica gel (petroleum/ethyl acetate=15:1 to 10:1) to provide the desired product.
97%	With 1-benzyl-4-aza-1-azoniabicyclo[2.2.2]octane dichromate In dichloromethane for 0.05h; Microwave irradiation;
97%	With methyltriphenylphosphonium peroxydisulfate In acetonitrile for 0.25h; Heating;
97%	With potassium permanganate In various solvent(s) at 20℃; for 1h;
97%	With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In neat (no solvent) at 20℃; for 0.75h; Milling;
97%	With tripotassium phosphate tribasic; copper (I) iodide; 1,10-Phenanthroline In 1,4-dioxane at 80℃; Schlenk technique;	General Procedure-2 [For the open air oxidation of alcohols to carbonyl compounds; GP-2(method B)]: General procedure: In an oven dried Schlenk tube, were added alcohol 1 (69.0-199.5 mg, 0.5 mmol), CuI (10 mol%)and 1,10-Phenanthroline (20 mol%) and K3PO4 (2 mmol) followed by the addition of dioxane (2mL) at room temperature under open air atmosphere. The stirred reaction mixture was heated inan oil bath at 80 C for 7-48 h. Progress of the reaction was monitored by TLC till the reaction iscompleted. Then, the reaction mixture was cooled to room temperature, quenched with aqueousNH4Cl solution and then extracted with CH2Cl2 (3 10 mL). The organic layer was washed withsaturated NaCl solution, dried (Na2SO4), and filtered. Evaporation of the solvent under reducedpressure and purification of the crude material by silica gel column chromatography (petroleumether/ethyl acetate) furnished the aldehyde/ketone 2 (61-97%).
97%	With dmap; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper trifluoromethanesulfonate; (S)-(-)-5-(2-pyrrolidinyl)-1H-tetrazole In acetonitrile 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 bismuth(III) chloride; benzyltriphenylphosphonium peroxymonosulfate In acetonitrile for 0.75h; Heating;
96%	With dihydrogen peroxide; 1-n-butyl-3-methylimidazolium tetrafluoroborate for 1.5h; Heating;
96%	With sodium (meta)periodate In dichloromethane; water monomer at 20℃; for 15h;
96%	In butanone Heating;
96.5%	With paraformaldehyd In toluene for 4h; Heating / reflux;	9 Operating as described in example 2, 5.0 g (0.03 mols) of veratric alcohol (3,4- dimethoxy benzyl alcohol) are reacted, in 50 g of toluene, with 2.25 g (0.075 mols of p-formaldehyde in the presence of 1.25 g of zirconia (ZrO2) XZO 632/03 fromMelcat.After filtering off the catalyst and evaporating under vacuum (at 30°C/21 mbar) a crude reaction product containing veratric aldehyde is obtained with a 96.5% GC yield and a conversion of 98.3%.
96%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; H₄VPO₇; oxygen In water monomer at 80℃; for 4h; Autoclave;
96%	With oxygen; 2,3-dicyano-5,6-dichloro-p-benzoquinone; NaNO₂ In dichloromethane; acetic acid at 20℃; for 6h;
96%	With dimanganese decacarbonyl In toluene at 120℃; for 12h; Sealed tube;
95%	With aluminum(III) oxide; potassium permanganate In neat (no solvent) for 0.0333333h;
95%	With benzyltriphenylphosphonium chlorochromate In dichloromethane for 0.0333333h; microwave irradiation;
95%	With benzyltriphenylphosphonium dichromate for 0.166667h;
95%	With potassium dichromate\|\|potassium bichromate\|\|K₂Cr₂O₇\|\|Cr₂O₇K₂; aluminium chloride anhydrous for 0.0333333h;
95%	With aluminium chloride anhydrous; butyltriphenylphosphonium periodate In acetonitrile for 9h; Heating;
95%	With 3,5-dimethylpyrazolium fluorochromate(VI) at 20℃; for 0.0333333h;
95%	With aluminium chloride anhydrous; 1-decyl-4-aza-1-azoniabicyclo[2.2.2]octane chlorochromate In acetonitrile for 1.5h; Heating;
95%	With benzyltriphenylphosphonium dichromate; mesoporous silica at 20℃; for 0.166667h;
95%	With NaNO₃ at 40℃; for 0.1h;
95%	With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In water monomer at 25℃; for 24h; Micellar solution;	General procedure for the oxidation of alcohols General procedure: A vial was charged with alcohol (1 mmol), IBX (1.2 mmol, 1.2 equiv) and 2 wt % GMPGS-2000/H2O solution (5 mL). The mixture was stirred for 24 h at 25 °C and filtered. The solid was washed with CH2Cl2 and the filtrate was extracted with CH2Cl2 (3×10 mL). Then, the organic phase was combined and dried with anhydrous Na2SO4, evaporated to dryness. The crude product was purified was purified by column chromatography on silica gel eluted with (petroleum ether/EtOAc) to afford the desired product.
95%	With Trametes villosa (viz. Poliporus pinsitus) laccase; oxygen; 6-methyl-1-hydroxybenzotriazole In 1,4-dioxane at 30℃; for 5h; Enzymatic reaction;	4.4 Enzymatic oxidations General procedure: The mediators 6-X-HBTs (10μmol), laccase from Trametes villosa (7-40 units) and the substrate (30 μmol) were added to a 5.0 mL of a buffered water solution (0.1M sodium citrate, pH 5.0) with 25% dioxane as cosolvent, purged with O2 for 30min before the addition of the reagents. The mixture was magnetically stirred at 30°C for 5-24 h under oxygen (filled balloon). Reaction products were extracted with ethyl acetate, characterized by GC-MS and 1H NMR and quantified by GC and 1H NMR analysis. A good material balance (>95%) was observed in all the experiments. In the absence of the mediator or the enzyme no formation of oxidation products was observed in significant amounts (<0.1%).
95%	With tert.-butylnitrite; oxygen; 2,3-dicyano-5,6-dichloro-p-benzoquinone In 2-methoxy-ethanol at 80℃; for 14h; chemoselective reaction;
95%	With dmap; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper chloride (I) In water monomer at 55℃; for 10h; Green chemistry;
95%	With 9-fluorenone In dimethyl sulfoxide at 20℃; Irradiation;
94%	With vanadyl(IV) acetylacetonate; oxygen; 1-n-butyl-3-methylimidazolium tetrafluoroborate at 80℃; for 12h;
94%	With nitric acid; diphosphorus pentoxide; mesoporous silica for 0.0333333h;
94%	With triphenylmethylphosphonium dichromate at 20℃; for 0.0666667h; Neat (no solvent); chemoselective reaction;
94%	With hydrogenchloride; 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; oxygen; nitric acid In water monomer; acetonitrile at 45℃; for 24h; High pressure; Sealed tube; chemoselective reaction;
94%	With oxygen In N,N-dimethyl-formamide at 20℃; for 6h; UV-irradiation;	Photocatalytic oxidation of benzyl alcohols by 3D-RGO/ZnO photocatalyst General procedure: A 25 mL round-bottomed flask was charged with alcohol (1 mmol),3D-RGO/ZnO (40 mg) and N,N-dimethyl formamide (5 mL). The resultant mixture was stirred under O2 with two white LED lamps (12W). After completion of the reaction, the 3D-RGO/ZnO catalyst was recycled by filtration and the organic phase of the filtrate was extracted with EtOAc, washed three times with water and dried over Na2SO4.The pure product was then isolated by silica chromatography using petroleum ether/EtOAc mixtures as the eluent.
94%	With 2,4,6-trimethyl-pyridine; 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; iodine; Sodium hydrogenocarbonate In dichloromethane; water monomer at 20 - 22℃; for 1h;	1.10 Preparative synthesis of compounds 2a,b,d-al (general procedure) 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.
93%	With aluminium chloride anhydrous; 1-benzyl-4-aza-1-azoniabicyclo[2.2.2]octane dichromate for 0.0111111h;
93%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper (II) acetate In water monomer; acetonitrile at 20℃; for 2h; Green chemistry;	General procedure: A mixture of alcohol (5.0 mmol), Cu(OAc)2 (9.1 mg, 0.05 mmol), and TEMPO (7.8 mg, 0.05 mmol) in CH3CN/H2O (5/10 mL) was stirred at room temperature for specified time. After completion of the reaction (monitored by TLC, eluents: petroleum ether/ethyl acetate = 4/1), dichloromethane (10 mL) was added to the resulting mixture. The dichloromethane phase was separated, and the aqueous phase was further extracted with dichloromethane (10 mL × 2). The combined organic layers were dried over anhydrous sodium sulfate and concentrated to give a residue, which was purified by column chromatography (eluents: petroleum ether/ethyl acetate = 10/1) to provide the desired product.
93%	With potassium carbonate In water monomer at 60℃; for 24h;	4.1. General Procedure for Heck Coupling and the Oxidationof Alcohols General procedure: A typical reaction was carried out as follows: bromobenzene(1a) (1.0 mmol), alkene (1.5 mmol), HCOONa (1.5mmol), 50 mg of wool-Pd complex catalyst (Pd 11.74 %),were added to 15 mL aqueous media (PEG-400 = 33 mg) ina 25 mL beaker, and stirred at 80 °C under ambient conditions.After the completion of the reaction, the catalyst was filtrated, washed and dried. Subsequently, 40 mg of the solid catalyst, benzyl alcohol (0.2 mmol), K2CO3 (0.2 mmol) were stirred in 15 mL aqueous media (PEG-400 = 33 mg), atmosphericair was used as the source of molecular oxygen at 60°C for 24 h, and the oxidation monitored by TLC. After completion, an extraction with ethyl acetate was performed.The organic layer was dried under reduced pressure to givethe desired crude product. Analytically pure products were obtained by column chromatography using petroleum ether and ethyl acetate as eluent. Formation of products and consumptionof substrates were monitored by GC. The identity of products was determined either by comparison with authentic samples using GC or by NMR analysis. The conversion and product selectivity were determined using GC analysis.
93%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; C₁₁₀H₂₀₂N₈O₄₇; oxygen; copper(II) bis(trifluoromethanesulfonate); potassium carbonate In water monomer at 20℃; for 6h; Green chemistry;	General procedure for aerobic oxidation of alcohols in water General procedure: To a 48 mL tube, were added Cu(II) or Cu(I) salt (0.05 mmol), PEG-PyTa (0.025 mmol) and H2O (3.0 mL). The mixture was stirred for 30 min at room temperature and a clear dark-blue solution was observed. Then alcohols (1.0 mmol), TEMPO (0.05 mmol), and K2CO3 (0.2 mmol) were sequentially added, followed by connecting a balloon of oxygen. The reaction mixture was stirred at room temperature until the reaction completed based on GC analysis. After that, the reaction mixture was extracted with MTBE (3 mL×3) and the extracts were combined, dried over anhydrous Na2SO4 and concentrated under vacuum. Finally, the residue was purified by flash chromatography on silica to afford the desired aldehydes.
93%	With sulfuric acid In dimethyl sulfoxide for 0.666667h; Reflux;	Protocol A: General procedure: A mixture of the benzylic alcohol 1 (1 mmol) and 98% H2SO4 (1 mmol) in DMSO (3 mL) was stirred for the appropriate time under reflux conditions. The mixture was then cooled to r.t., and brine (4 mL) was added. The organic phase was extracted with CH2Cl2 (6 mL), and the organic layer was dried (Na2SO4), filtered, and concentrated under reduced pressure. In all cases, the reaction products were obtained with high purity, and did not require further purification by distillation or column chromatography.
92%	With mesoporous silica; pyridinium chlorochromate In dichloromethane at 18℃; for 0.333333h;
92%	With laccase; oxygen; benzotriazol-1-ol In various solvent(s) at 20℃; for 24h;
92%	With hydrogenchloride; 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; oxygen; nitric acid In water monomer; acetonitrile at 45℃; for 24h; Sealed tube;	3,4-Dimethoxy-benzaldehyde (3a) General procedure: To a 25 mL high pressure tube with a stir bar was added lignin model compound (1 mmol) and 5 mol % of NHAc-TEMPO (0.05 mmol, 10.6 mg). The tube was sealed, evacuated and filled to 1.1 atm with oxygen gas. Nitric acid (67%; 9.4 μL) (0.1 mmol, 6.3 mg) in 1 mL acetonitrile and 9.9 μL of hydrochloric acid (37%) (0.1 mmol, 3.65 mg) in 1 mL of acetonitrile was injected through the septum individually. Additional 3 mL of acetonitrile and 260 μL of water were injected. The reaction mixture was stirred for 24 h at 45° C. The solvent was evaporated and the residue was subjected to column chromatography to ascertain the amount of the corresponding carbonyl compound. The reaction of 1 with optimized catalyst system was repeated several times. The results are shown in FIG. 5. As is clearly depicted in the figure, the conversion and yield results for this catalytic system (HNO3/HCl/NHAc-TEMPO) are highly consistent. The six identical runs yielded statistically identical conversions and yields. Spectral data were consistent with those reported in the literature. (Jeena, V.; Robinson, R. S. Chem. Commun. 2012, 48, 299.) 1H NMR (400 MHz, CDCl3) δ 9.86 (s, 1H), 7.47 (dd, J=8.2, 2.0 Hz, 1H), 7.41 (d, J=1.8 Hz, 1H), 6.97 (d, J=8.2 Hz, 1H), 3.97 (s, 3H), 3.95 (s, 3H). HRMS (EI) calculated for C9H10O3 [M]+ 166.0630. found 166.0626.
92%	With hydrogenchloride; 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; oxygen; nitric acid In water monomer; acetonitrile at 45℃; for 24h; Sealed tube;	3a General Procedure for Oxidation of Lignin Model Compounds General Procedure for Oxidation of Lignin Model Compounds: (0198) To a 25 mL high pressure tube with a stir bar was added lignin model compound (1 mmol) and 5 mol of NHAc-TEMPO (0.05 mmol, 10.6 mg). The tube was sealed, evacuated and filled to 1.1 atm with oxygen gas. Nitric acid (67%; 9.4 μΕ) (0.1 mmol, 6.3 mg) in 1 mL acetonitrile and 9.9 μΕ of hydrochloric acid (37%) (0.1 mmol, 3.65 mg) in 1 mL of acetonitrile was injected through the septum individually. Additional 3 mL of acetonitrile and 260 μL· of water were injected. The reaction mixture was stirred for 24 h at 45°C. The solvent was evaporated and the residue was subjected to column (0199) chromatography to ascertain the amount of the corresponding carbonyl compound. The reaction of 1 with optimized catalyst system was repeated several times. The results are shown in Fig. 5. As is clearly depicted in the figure, the conversion and yield results for this catalytic system (HNO3/HCI/NHAC-TEMPO) are highly consistent. The six identical runs yielded statistically identical conversions and yields.
91%	With 4-(N,N-dimethylamino)pyridinium chlorochromate In dichloromethane for 14h;
91%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen; copper (II) acetate; diethylamine In acetonitrile at 50℃; for 3h; chemoselective reaction;	General procedure for synthesis of carbonyl compounds General procedure: A mixture of an alcohol (5.0 mmol), Cu(OAc)2*H2O (50 mg, 5 mol%), TEMPO (39 mg,5 mol%) and diethylamine (25 μL, 5 mol%) in CH3CN (10 mL) was stirred at 50°C under oxygen balloon for a specified time as noted in the Table I. For the analysis of the products, gas chromatography (equipped with a Capillary Column of VF-1 ms, 15 m,0.25 mm, 0.25 μm) was employed. Time-to-time quantification of the reactants consumed and products generated was examined by GC by comparing the peak area with the standard starting alcohol and the product. After a specified time, the reaction mixture was passed through a celite pad and washed with acetonitrile, and concentrated to get the crude, which was purified by column chromatography (hexane/ethyl acetate = 4.75/0.25) to obtain the desired product.
90%	With n-butyltriphenylphosphonium permanganate In acetonitrile at 20℃; for 0.333333h;
90%	With iodine; potassium carbonate; potassium iodide at 90℃; for 0.416667h;
90%	With potassium peroxodisulfate at 40℃; for 0.0833333h; Ionic liquid;
90%	With ferric(III) chloride; nitric acid In acetone at 20℃; for 0.416667h; Sonication;
90%	With ammonium cerium (IV) nitrate; 1-hexyl-3-methylimidazolium hydrogen sulfate at 80℃; for 0.333333h; neat (no solvent); chemoselective reaction;
90%	With C₁₈H₂₆Cl₂Cu₃N₄O₁₀; dihydrogen peroxide In neat (no solvent) at 100℃; for 5h;
90%	With tripotassium phosphate tribasic; carbon dioxide In dimethyl sulfoxide at 90℃; for 48h;
89%	With dmap; oxygen In various solvent(s) at 20℃; for 5h;
89%	With dihydrogen peroxide; manganese(II) acetate In n-heptane; water monomer at 25℃; for 0.5h; Ionic liquid; chemoselective reaction;	2.3 General procedures for the oxidation of alcohols General procedure: To a 25 mL round-bottom flask, ionic liquid (5.6 mmol), Mn(OAc)2 (0.025 mol%), alcohol (3 mmol), and n-heptane (6 mL) were added. De-ionized water (0.5 mL) was added to lower the viscosity of the mixture. The resulting solution was then kept stirring vigorously. Under ambient conditions, aqueous hydrogen peroxide (6× 60 μL, 35 wt.% in water) was injected into the reaction mixture in 3 min intervals over 20 min. After the reaction had been completed, the n-heptane solution (upper layer) was carefully decanted from the ionic liquid medium. In order to completely extract the aldehyde from the ionic liquid with residual n-heptane, additional n-heptane (2× 5 mL) was added and the combined organic solution was then dried over anhydrous sodium sulfate. After the removal of solvent under vacuum, the aldehyde was isolated as a colourless liquid and characterized by GC-MS and 1H NMR. The n-heptane collected was reused in catalysis and extraction process. It was found that the use of n-heptane, n-hexane, n-pentane, or petroleum ether (40-60 °C) as the extraction phase in the catalysis showed no observable difference as these solvents are immiscible with the ionic liquid. However, heptane was chosen because it is considered as a greener alternative solvent for chemical processes [20].
89%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; anhydrous sodium carbonate; N-Phenylglycine; copper (II) bromide In water monomer for 1h; Reflux; Schlenk technique;	General Procedures for the Copper-Catalyzed Primary BenzylicAlcohol Oxidation under Air in Water (p-MethylbenzylAlcohol) General procedure: A mixture of p-methylbenzyl alcohol (1.0 mmol), N-phenylglycine(0.0076 g, 0.05 mmol), CuBr2 (0.0112 g, 0.05 mmol),Na2CO3 (0.1060 g, 1.0 mmol), TEMPO (0.0078 g, 0.05 mmol),H2O (3.0 mL) were added to a 100 mL Schlenk tube, which wasvigorously stirred in air under reflux for 0.5 h. After the reaction,the product was extracted with CH2Cl2 (3 × 2.0 mL). Thecombined organic phase was washed with H2O (3.0 mL) anddried over anhydrous MgSO4. After concentration undervacuum, the residue was purified by column chromatography toafford p-methylbenzaldehyde.Isolated yield: 0.1080 g (90%).
89%	With iodine In water monomer; dimethyl sulfoxide at 100℃; for 3h; chemoselective reaction;	Procedure General procedure: A mixture of benzyl alcohol (0.108 g, 1 mmol), I2 (0.279 g, 1.1 mmol) in DMSO (1 mL)and water (2 mL) was stirred at 100 C for 3 h. Then, the reaction mixture was cooledto room temperature. To the reaction mixture was added 2mL of aqueous sodium thiosulfatesolution and the organic phase was extracted with 5mL of dichloromethane.Finally, the organic layer was dried over anhydrous Na2SO4, filtered and the solventwas removed under reduced pressure. In all cases, the reaction products were obtainedin high purity, and did not require further purification by distillation or columnchromatography
88%	With ammonium nitrate In dichloromethane at 20℃; for 0.416667h;
88%	With 1-methyl-1H-imidazole; copper (I) iodide; C₂₀H₂₅N₄O₂ In acetonitrile at 25℃; for 1.5h;
88%	With 2C₃₆H₆₀N₉⁽³⁺⁾*3O₄W^(2-); dihydrogen peroxide In water monomer at 20℃; for 0.166667h; Green chemistry;
88%	With C₆H₄MoNO₇^(1-)*C₁₉H₄₂N⁽¹⁺⁾; oxygen In water monomer at 100℃; for 18h; Green chemistry; chemoselective reaction;	2.3. General procedure for the catalytic oxidation of alcohols toaldehydes General procedure: A mixture of alcohol (0.75 mmol), and catalyst Mo1 (13 mg,3.0 mol%) taken in 0.5 mL of water was stirred at 100 ° C under oxygenatmosphere (O2 bladder) and the stirring was continued for16-24 h as per requirement. The progress of reaction was monitoredby TLC. After completion of the reaction, ethyl acetate was added to the mixture. The aqueous phase was extracted with ethyl acetate 2-3 times. Then the combined organic extracts were driedover anhydrous sodium sulfate and the solvent was removed under reduced pressure. The crude product so obtained was purified by column chromatography using hexane-ethyl acetate as eluent. While the known products were characterized by spectroscopic techniques and compared with reported data and the new products 22b and 36b were characterized completely. The characterization detail is provided in supporting information section.
88%	With NiCl2/γ-Al2O3; potassium-t-butoxide In toluene at 80℃; for 7h; chemoselective reaction;
88%	With potassium peroxodisulfate; V₂O₅/TiO₂ In water monomer; acetonitrile at 80℃; Sealed tube; Green chemistry;
87%	With 2,2,6,6-tetramethyl-1-piperidinyloxy free radical; silver(I) nitrate In water monomer for 10h; UV-irradiation;
87%	With bis(diphenylphosphonium)ferrocene perruthenate grafted on SiO₂ coated Fe₃O₄ magnetic nanoparticles In tetrahydrofuran for 4h; Reflux;	General Procedure for Oxidation of Alcohol General procedure: A primary alcohol (1 mmol) was added to a suspension of 50 mg of [DppfSilNMag](RuO4)2 8 in 5mL of THF and refluxed. TLC was used to monitor the reaction progress. Compound 8 was isolated magnetically after completion of the reaction. Column chromatography (ethyl acetate/petroleum ether) wasused to purify the reaction mixture to afford pure products.
86%	With aluminium chloride anhydrous; benzyltriphenylphosphonium periodate In acetonitrile for 3.33333h; Heating;
86%	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 water monomer at 20℃; for 7h; Green chemistry;
86%	With ferrocene-labeled Merrifield resin-supported ionic liquid ([FemDMMerA]RuO₄) In tetrahydrofuran for 5h; Reflux; Green chemistry;	General procedure for the oxidation of alcohols General procedure: A mixture of aryl alcohol (1 mmol) and [FemDMMerA]Y (100 mg) in solvent(5 mL) was refluxed in oil bath. After completion of the reaction as monitored byTLC, the reaction mixture was filtered to remove insoluble SILP catalyst.Evaporation of solvent in vacuuo followed by column chromatography over silicagel using petroleum ether/ethyl acetate (95:5 v/v) afforded pure aldehydes.
85%	With oxygen; potassium carbonate In toluene at 90℃; for 10h;
84%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; C₂₀H₃₆N₅⁽³⁺⁾*3Br^(1-); oxygen; copper atom In water monomer at 35℃; for 12h; Schlenk technique;	Cu/L₂/TEMPO-Catalyzed Aerobic Oxidation of Benzylic Alcohols; General Procedure General procedure: A 30-mL Schlenk tube was evacuated and filled with O2, the benzyl alcohol (1 mmol), Cu powder (5% mol), imidazolium (5% mol), TEMPO (5% mol), and H2O (3 mL) was added and stirred at 35 °C under an O2 atmosphere by connecting an O2 balloon. When the reaction was complete, the mixture was extracted with CH2Cl2 (3 × 10 mL). The combined extracts were dried (MgSO4). Then the solvent was removed and the mixture was purified by column chromatography (silica gel) to give the product.
83%	With tripotassium phosphate tribasic; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; Cu₂(phenanthroline)₂(μ-Cl)₂Cl₂; oxygen In acetonitrile at 20℃; for 2h;
83%	With palladium; oxygen; Sodium hydrogenocarbonate In water monomer at 80℃; for 2h;	2.7 Vanillic Alcohol, Veratryl AlcoholandHydrobenzoin Oxidations The reactions were performed in a 100mL round-bottomedflask. A colloidal suspension of PVP stabilized Pd NPs(20mL, 7.05 × 10-5mol of Pd), or a dispersion of Pd/TiO2(277mg, 7.05 × 10-5mol Pd) in 20mL of HPLC-gradewater, was introduced in the flask. NaHCO3(400mg) wasadded and the mixture heated at 80°C under vigorous stirring.The reactant (7.05 × 10-3mol for vanillic and veratrylalcohol, 100 equiv./Pd or 7.05 × 10-4mol for hydrobenzoin,10 equiv./Pd) was then added. The mixture was heated atthe desired temperature stirred under air or O2flow, for adetermined time with regular sampling for analysis.
82%	With acetic anhydride; NaNO₂ at 25℃;
82%	With copper chloride (II) In tetrahydrofuran at 80℃; for 1.5h; chemoselective reaction;
82%	With [RuCl₂(p-cymene)(1,4-dibutyl-3-methyl-1,2,3-triazolylidene)] In toluene at 110℃; for 16h;
82%	With dmap; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper (II) acetate In neat (no solvent) at 25℃; for 36h; Green chemistry;
82%	With chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II); oxygen In tetrahydrofuran for 0.48h; Reflux;
81%	With C₂₃H₃₅N₃O₃⁽¹⁺⁾*Br^(1-); copper atom In chlorobenzene at 80℃; for 15h;
80%	With 3 A molecular sieve; pyridinium chlorochromate In dichloromethane at 25℃; for 0.166667h;
80%	With 3 Angstroem MS; pyridinium chlorochromate In dichloromethane for 0.166667h;
80%	With [Cu₃(1,3,5-benzenetricarboxylate)₂]; 9-azabicyclo<3.3.1>nonane-N-oxyl; oxygen In 1,2-dichloro-ethane at 70℃; for 15h; Green chemistry;	5. General procedures of the aerobic oxidation catalyzed by HKUST-1/ABNO 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
80%	With C₁₅H₂₅Cl₂N₃NiO₃; potassium-t-butoxide In toluene at 110℃; for 12h; Schlenk technique; Inert atmosphere;

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4
[ 93-03-8 ]
[ 7306-46-9 ]

Yield	Reaction Conditions	Operation in experiment
100%	With thionyl chloride;	b 3,4-Dimethoxybenzyl chloride STR32 To 3,4-dimethoxybenzyl alcohol (4.96 g, 0.029 mol) was added thionyl chloride (6.45 ml, 0.088 mol) and the mixture was heated under reflux for 20 minutes. The reaction mixture was poured into ice-water and extracted with chloroform. After drying over anhydrous magnesium sulfate and decoloring with active charcoal, the solvent was distilled off to give 5.50 g of the title compound as an oily substance. Yield=100%. 1 H-NMR(CDCl3)delta3.89(s,3H), 3.90(s,3H), 4.57(s,2H), 6.83(d,J=8 Hz,1H), 6.90-6.95(m,2H)
24%	With pyridine; thionyl chloride; In dichloromethane; at 0℃; for 2h;	To a 0 oc cooled solution of (3,4-dimethoxyphenyl)methanol (10 g,59.5 mmol) and pyridine (4.81 mL, 59.5 mmol) in dichloromethane (300 mL) was addeddrop wise thionyl chloride (4.34 mL, 59.5 mmol) and the reaction mixture was stirred at 0 ocfor 2 hours. Water was added and the organic layer was separated and then dried overMgS04. The solvent was evaporated and the crude material was purified via silica gelchromatography to give 4-(chloromethyl)-1 ,2-dimethoxybenzene (2.66 g, 14.27 mmol, 24%yield). 1H NMR (400 MHz, CHLOROFORM-d) o ppm 6.91-6.99 (m, 2 H), 6.84 (d, J=8.1 Hz,1 H), 4.58 (s, 2 H), 3.90 (d, J=7.3 Hz, 6 H).
	With thionyl chloride; In dichloromethane;	i 3,4-Dimethoxybenzyl chloride In a nitrogen atmosphere, 5 g (29.73 mmol.) of 3,4-dimethoxybenzyl alcohol was dissolved in 25 ml of dichloromethane. The obtained solution was placed in an ice-bath, and to this was dropwise added a solution of 2.16 ml (29.74 mmol.) of thionyl chloride in 5 ml of methylene chloride. The mixture was then stirred at room temperature for 1 hour. The mixture was placed under reduced pressure at room temperature to distill off the solvent to give 5.624 g of the desired compound as a yellow oil. 1 H-NMR (CDCl3) delta:3.86 (s, 3H), 3.88 (s, 3H), 4.57 (s, 2H), 6.7-7.0 (m, 3H).

	With thionyl chloride; In dichloromethane; water;	(1) 235 g of veratryl alcohol was dissolved in 1.4 l of absolute methylene chloride, to which 200 g of thionyl chloride was added dropwise while ice-cooling, and the mixture was stirred at room temperature overnight. Dark brown and clear solution was poured into 1 l of ice-cold water and was adjusted to pH 7.0 with sodium bicarbonate. The methylene chloride layer was separated, washed with water, dehydrated and concentrated to dryness under reduced pressure to obtain 220 g of 3,4-dimethoxybenzyl chloride. m.p. 50-51 C.
	With thionyl chloride; In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; dichloromethane;	(1) To a solution of 235 g of veratryl alcohol in 1.4 liters of dry methylene chloride, 200 g of thionyl chloride was added dropwise while cooling with ice, and the mixture was stirred at room temperature overnight. The resulting dark brown reaction solution was poured into one liter of ice water. The pH of the solution was adjusted to 7.0 with sodium bicarbonate. The methylene chloride layer was separated, washed with water, dehydrated, and concentrated to dryness under vacuum to obtain 220 g of 3,4-dimethoxybenzyl chloride having a melting point of 50 to 51 C.
	With thionyl chloride; In toluene; at 0℃; for 1h;	3,4-dimethoxybenzyl alcohol [(20] g, 119 mmol) was dissolved in toluene (60 ml) and cooled to [0C.] Thionyl chloride (7.48 g, 61.4 mmol) was added dropwise to the cooled solution of the alcohol over a period of 30 minutes, and the reaction was maintained at [0C] for an additional 30 minutes. The reaction was quenched by pouring onto an ice/water mix (100 ml), and the organic phase was separated. The aqueous phase was then extracted into toluene (2 x 20 [ML)] and the combined toluene solution was dried over anhydrous sodium sulfate. The toluene was removed at reduced pressure to afford an oil which solidified upon standing, with a yield of 21 g. The material was characterized as a single spot by thin layer chromatography [(TLC).]
	With thionyl chloride; In dichloromethane; for 1h;Heating / reflux;	A solution of 3, 4-dimethoxy-benzyl alcohol (1.5 g) in anhydrous DCM (5 mL) was dropped into a solution of thionyl chloride (1.3 mL) in anhydrous DCM (6 mL) under a Nitrogen atmosphere. The solution was heated to reflux for 1 hour, then allowed to cool to r. t. and concentrated in vacuo. The residue was purified by flash chromatography (CH/AcOEt 6: 4) to give the title compound (1.63 g) as a white solid. T. [I. C.] : CH/AcOEt 6: 4, R=0.63. [NMR (CDCI3)] : [5] (ppm) 7.94 (dd, 1H) ; 6.92 (d, 1H) ; 6.83 (d, 1H) ; 4.57 (s, 2H); 3.9 (s, 3H); 3.89 (s, 3H). MS [(EL/+)] : m/z=186 [MH] +.
	With thionyl chloride; triethylamine; In dichloromethane; at 20℃; for 3h;	General procedure: To asolution of 2a (8.3 g, 0.037 mol) in DCM (10 mL), Et3N (6.2 mL,0.043 mol), SOCl2 (3.0 mL, 0.043 mol) was slowly dropped under icesalt bath. After stirred at room temperature for 3 h, the solution waswashed with diluted water (10 mL×3).

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5
[ 110-87-2 ]
[ 93-03-8 ]
[ 148625-44-9 ]

Yield	Reaction Conditions	Operation in experiment
95%	With tin(ll) chloride In chloroform for 0.333333h; Ambient temperature;
94%	With mesoporous p-hydroxybenzenesulphonic acid-formaldehyde polymer resin In neat (no solvent) at 20℃; for 2h; chemoselective reaction;	2.3. Typical procedure for tetrahydropyranylation of alcohol using PAFR catalyst General procedure: As a pilot protocol, a mixture of 1-octanol (0.130 g, 1 mmol), DHP (0.084 g, 2 mmol) and PAFR catalyst (0.025 g, 7.48 mol%) was mechanically stirred in a small reaction vessel at room temperature. The progress of the reaction was monitored by thin layer chromatography (TLC). After completion of the reaction as indicated by TLC, the catalyst was separated by simple filtration and the reaction mixture was extracted with ethyl acetate, the extracted compound thus obtained was then charged into a short silica gel chromatography column using hexane/ethyl acetate (9:1 ratio) as eluent to afford 98% of isolated yield of desired product.
90%	With copper dichloride In dichloromethane Ambient temperature;

89%	With ammonium cerium(IV) nitrate In acetonitrile for 0.5h; Ambient temperature;
89%	With P-benzyltriphenylphosphonium tribromide In dichloromethane at 20℃; for 0.166667h;
83%	With iodine In dichloromethane for 1h;
80%	With pyridine hydrochloride at 20℃; for 0.05h; Neat (no solvent);
80 %Chromat.	With acetic acid at 20℃; for 2h;

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[8]Location in patent: experimental part Narender; Suresh Kumar Reddy; Arun Kumar; Rohitha; Kulkarni [Catalysis Letters, 2010, vol. 134, # 1-2, p. 175 - 178]

6
[ 124-38-9 ]
[ 93-03-8 ]
[ 569-31-3 ]

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7
[ 93-03-8 ]
[ 494-99-5 ]

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8
[ 93-03-8 ]
[ 53207-00-4 ]

Yield	Reaction Conditions	Operation in experiment
100%	With bromine In acetic acid at 20℃; for 1h;	210.a A mixture of [3,4-bis(methyloxy)phenyl]methanol (0.84 g, 5mmol), Br2 (0.4 mL) and AcOH (4 m N concentrated to yield the product (1.66 g, 100%) as a clear oil. 1H-NMR (CDCl3) δ : 3.891 (d, 6H, J= 3.2 Hz), 4.601 (s, 2H), 6.941 (s, IH), 7.029 (s, IH).
95%	With bromine; acetic acid at 25℃;
95%	With bromine; acetic acid at 0 - 20℃;

95%	Stage #1: (3,4-dimethoxyphenyl)methanol With acetic acid at 0℃; for 0.5h; Stage #2: With bromine; acetic acid at 0 - 20℃;	2 PREPARATION 2 1-bromo-2-(bromomethyl)-4,5-dimethoxybenzene Based on Chem. Eur. J. 2010, 16, 9772-9776 [0029] To a solution of (3,4-dimethoxyphenyl)methanol (101.5 mmoles, 14.85 mL, 1 eq.) in 80 mL of glacial acetic acid there are added, at 0° C., over 30 minutes, 6 mL of dibromine (116.8 mmoles, 1.15 eq.) in 18 mL of glacial acetic acid. The reaction mixture is stirred for 3 hours and then brought back to ambient temperature. Stirring is stopped in order to allow the 1-bromo-2-(bromomethyl)-4,5-dimethoxybenzene to precipitate completely overnight. The precipitate is filtered off, washed with methanol and recrystallised from methanol to yield 29.9 g of a light-yellow powder. [0030] Yield=95%
92%	With bromine In chloroform for 1h; Ambient temperature;
91%	With bromine In chloroform at 60℃; for 6h;
84%	With bromine; acetic acid at 20℃; for 0.833333h;
67%	With bromine In chloroform at 0 - 20℃; for 2h; Schlenk technique; Inert atmosphere;

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9
[ 93-03-8 ]
[ 93-07-2 ]

Yield	Reaction Conditions	Operation in experiment
98%	With tert.-butylhydroperoxide; vanadia In water at 100℃; for 8h;	4.3. Typical experimental procedure for oxidation of alcohols General procedure: To a well-stirred suspension of alcohol (1 mmol) and V2O5 (0.05 mmol) in water (1 mL) was added aq TBHP (70%, 4 mmol). The reaction mixture was heated at reflux until the completion of the reaction (monitored by TLC). The reaction mixture was extracted with ethyl acetate (3×15 mL). The combined organic layer was dried over Na2SO4 and evaporated under vacuum to furnish the crude product, which was purified on a silica gel column using EtOAc and hexane as the solvent mixture. In case of problem in isolating the acid, the solvent was evaporated under vacuum and the crude residue was purified by column chromatography on silica gel (EtOAc/hexane).
91%	With tert.-butylhydroperoxide; copper(ll) bromide In water; acetonitrile at 20℃; for 1.5h; Inert atmosphere;
89%	With tert.-butylhydroperoxide; bismuth(III) oxide In water; ethyl acetate for 31h; Reflux; chemoselective reaction;

88%	With tert.-butylhydroperoxide; ammonium cerium (IV) nitrate In water; acetonitrile at 20℃; for 18h; chemoselective reaction;
84%	Stage #1: (3,4-dimethoxyphenyl)methanol With C₂₉H₄₄Cl₂N₂Ru; sodium hydroxide In water for 24h; Reflux; Stage #2: With hydrogenchloride In water
76%	With tert.-butylhydroperoxide; N-hydroxyphthalimide; oxygen In acetonitrile at 80℃; for 36h;
72%	Stage #1: (3,4-dimethoxyphenyl)methanol With Ru(η(2)-2-(2'-pyridyl)phenyl)Cl(CO)(PPh3)2; potassium hydroxide In toluene at 120℃; for 6h; Schlenk technique; Inert atmosphere; Stage #2: With hydrogenchloride In water
66%	With sodium hydroxide; osmium(VIII) oxide; sulfuric acid; potassium hexacyanoferrate(III) In water for 3h; Ambient temperature;
50%	Stage #1: (3,4-dimethoxyphenyl)methanol With 1-hexene; Pd/SiO₂; [Rh(trop2NH)(PPh₃)]OTf; water; sodium hydroxide at 20℃; for 12h; Inert atmosphere; Stage #2: With hydrogenchloride In water Inert atmosphere;
17%	With 1,4-diaza-bicyclo[2.2.2]octane; oxygen at 95℃; for 24h;
	With sodium periodate; <Ru(OH)2<IO5(OH)>2>(6-); sulfuric acid 1) aq. KOH, rt, 3 h; Yield given. Multistep reaction;
	With manganese(II) sulfate; Trametes hirsuta laccase aq. Na-oxalate buffer; Enzymatic reaction;
	Multi-step reaction with 5 steps 1.1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; oxygen; nitric acid; hydrogenchloride / water; acetonitrile / 24 h / 45 °C / High pressure; Sealed tube 2.1: lithium diisopropyl amide / tetrahydrofuran 2.2: -78 - 20 °C 3.1: sodium tetrahydroborate / tetrahydrofuran; water 4.1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; oxygen / water; acetonitrile / Sealed tube 4.2: 9 h / 45 °C 5.1: sodium hydroxide; dihydrogen peroxide / tetrahydrofuran; methanol / 10 h / 50 °C
	Multi-step reaction with 5 steps 1.1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; oxygen; nitric acid; hydrogenchloride / water; acetonitrile / 24 h / 45 °C / High pressure; Sealed tube 2.1: lithium diisopropyl amide / tetrahydrofuran 2.2: -78 - 20 °C 3.1: sodium tetrahydroborate / tetrahydrofuran; water 4.1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; sodium nitrite / water; acetic acid / 12 h / 20 °C / 760.05 Torr 5.1: sodium hydroxide; dihydrogen peroxide / tetrahydrofuran; methanol / 10 h / 50 °C
	Multi-step reaction with 5 steps 1.1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; oxygen; nitric acid; hydrogenchloride / water; acetonitrile / 24 h / 45 °C / High pressure; Sealed tube 2.1: lithium diisopropyl amide / tetrahydrofuran 2.2: -78 - 20 °C 3.1: sodium tetrahydroborate / tetrahydrofuran; water 4.1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; sodium nitrite / water; acetic acid / 24 h / 20 °C / 760.05 Torr 5.1: sodium hydroxide; dihydrogen peroxide / tetrahydrofuran; methanol / 10 h / 50 °C
	Multi-step reaction with 2 steps 1: sodium hydroxide; meta-dinitrobenzene / water / 2.5 h / 100 °C / Sealed tube 2: sodium hydroxide; meta-dinitrobenzene / water / 2.5 h / 100 °C / Sealed tube
	Multi-step reaction with 3 steps 1: phosphorus tribromide / dichloromethane / 4 h / 20 °C / Schlenk technique 2: sodium carbonate / N,N-dimethyl-formamide / 25 °C 3: [bis(acetoxy)iodo]benzene; Fe(TAML)Li; diphenylether; water / acetone / 1 h / 25 °C / Green chemistry
	Multi-step reaction with 5 steps 1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogenchloride; oxygen / acetonitrile; water / 24 h / 45 °C / 836.06 Torr / Sealed tube 2: lithium diisopropyl amide / tetrahydrofuran / -78 - 20 °C 3: water; sodium tetrahydroborate / tetrahydrofuran 4: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogen bromide / acetonitrile; water / 24 h / 20 °C 5: sodium hydroxide; dihydrogen peroxide / tetrahydrofuran; methanol / 4 h / 70 °C / pH 10
	Multi-step reaction with 5 steps 1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogenchloride; oxygen / acetonitrile; water / 24 h / 45 °C / 836.06 Torr / Sealed tube 2: lithium diisopropyl amide / tetrahydrofuran / -78 - 20 °C 3: water; sodium tetrahydroborate / tetrahydrofuran 4: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogen bromide / acetonitrile; water / 24 h / 20 °C 5: sodium hydroxide; dihydrogen peroxide / tetrahydrofuran; methanol; water / 10 h / 50 °C
	Multi-step reaction with 5 steps 1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogenchloride; oxygen / acetonitrile; water / 24 h / 45 °C / 836.06 Torr / Sealed tube 2: lithium diisopropyl amide / tetrahydrofuran / -78 - 20 °C 3: water; sodium tetrahydroborate / tetrahydrofuran 4: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogenchloride; oxygen / acetonitrile; water / 20 h / 45 °C / 760.05 Torr 5: sodium hydroxide; dihydrogen peroxide / tetrahydrofuran; methanol / 4 h / 70 °C / pH 10
	Multi-step reaction with 5 steps 1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogenchloride; oxygen / acetonitrile; water / 24 h / 45 °C / 836.06 Torr / Sealed tube 2: lithium diisopropyl amide / tetrahydrofuran / -78 - 20 °C 3: water; sodium tetrahydroborate / tetrahydrofuran 4: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogenchloride; oxygen / acetonitrile; water / 20 h / 45 °C / 760.05 Torr 5: sodium hydroxide; dihydrogen peroxide / tetrahydrofuran; methanol; water / 10 h / 50 °C
	Multi-step reaction with 5 steps 1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogenchloride; oxygen / acetonitrile; water / 24 h / 45 °C / 836.06 Torr / Sealed tube 2: lithium diisopropyl amide / tetrahydrofuran / -78 - 20 °C 3: water; sodium tetrahydroborate / tetrahydrofuran 4: acetic acid; 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid / water / 24 h / 20 °C 5: sodium hydroxide; dihydrogen peroxide / tetrahydrofuran; methanol / 4 h / 70 °C / pH 10
	Multi-step reaction with 5 steps 1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogenchloride; oxygen / acetonitrile; water / 24 h / 45 °C / 836.06 Torr / Sealed tube 2: lithium diisopropyl amide / tetrahydrofuran / -78 - 20 °C 3: water; sodium tetrahydroborate / tetrahydrofuran 4: acetic acid; 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid / water / 24 h / 20 °C 5: sodium hydroxide; dihydrogen peroxide / tetrahydrofuran; methanol; water / 10 h / 50 °C
	Multi-step reaction with 5 steps 1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogenchloride; oxygen / acetonitrile; water / 24 h / 45 °C / 836.06 Torr / Sealed tube 2: lithium diisopropyl amide / tetrahydrofuran / -78 - 20 °C 3: water; sodium tetrahydroborate / tetrahydrofuran 4: acetic acid; 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; sodium nitrite / water / 22 h / 20 °C 5: sodium hydroxide; dihydrogen peroxide / tetrahydrofuran; methanol / 4 h / 70 °C / pH 10
	Multi-step reaction with 5 steps 1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogenchloride; oxygen / acetonitrile; water / 24 h / 45 °C / 836.06 Torr / Sealed tube 2: lithium diisopropyl amide / tetrahydrofuran / -78 - 20 °C 3: water; sodium tetrahydroborate / tetrahydrofuran 4: acetic acid; 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; sodium nitrite / water / 22 h / 20 °C 5: sodium hydroxide; dihydrogen peroxide / tetrahydrofuran; methanol; water / 10 h / 50 °C
	Multi-step reaction with 5 steps 1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogenchloride; oxygen / acetonitrile; water / 24 h / 45 °C / 836.06 Torr / Sealed tube 2: lithium diisopropyl amide / tetrahydrofuran / -78 - 20 °C 3: water; sodium tetrahydroborate / tetrahydrofuran 4: potassium carbonate; oxygen; sodium hydroxide; iron(III)-acetylacetonate; 1,10-Phenanthroline / toluene / 20 h / 60 °C / 760.05 Torr 5: sodium hydroxide; dihydrogen peroxide / tetrahydrofuran; methanol / 4 h / 70 °C / pH 10
	Multi-step reaction with 5 steps 1: 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; nitric acid; hydrogenchloride; oxygen / acetonitrile; water / 24 h / 45 °C / 836.06 Torr / Sealed tube 2: lithium diisopropyl amide / tetrahydrofuran / -78 - 20 °C 3: water; sodium tetrahydroborate / tetrahydrofuran 4: potassium carbonate; oxygen; sodium hydroxide; iron(III)-acetylacetonate; 1,10-Phenanthroline / toluene / 20 h / 60 °C / 760.05 Torr 5: sodium hydroxide; dihydrogen peroxide / tetrahydrofuran; methanol; water / 10 h / 50 °C
	With phosphoric acid; dihydrogen peroxide; sodium hydroxide In water at 50℃; for 6.5h;
	With oxygen; potassium hydroxide In neat (no solvent) at 100℃; for 3h;

Reference： [1]Location in patent: experimental part Alagiri, Kaliyamoorthy; Prabhu, Kandikere Ramaiah [Tetrahedron, 2011, vol. 67, # 44, p. 8544 - 8551]
[2]Location in patent: experimental part Das, Rima; Chakraborty, Debashis [Applied Organometallic Chemistry, 2011, vol. 25, # 6, p. 437 - 442]
[3]Location in patent: experimental part Malik, Payal; Chakraborty, Debashis [Synthesis, 2010, # 21, p. 3736 - 3740]
[4]Location in patent: experimental part Gowda, Ravikumar R.; Chakraborty, Debashis [Chinese Journal of Chemistry, 2011, vol. 29, # 11, p. 2379 - 2384]
[5]Malineni, Jagadeesh; Keul, Helmut; Möller, Martin [Dalton Transactions, 2015, vol. 44, # 39, p. 17409 - 17414]
[6]Zhang, Jian; Liu, Yu; Chiba, Shunsuke; Loh, Teck-Peng [Chemical Communications, 2013, vol. 49, # 97, p. 11439 - 11441]
[7]Gong, Dawei; Hu, Bowen; Chen, Dafa [Dalton Transactions, 2019, vol. 48, # 24, p. 8826 - 8834]
[8]Bailey, Alan J.; Bhowon, Minu G.; Griffith, William P.; Shoair, Abdel G. F.; White, Andrew J. P.; Williams, David J. [Journal of the Chemical Society, Dalton Transactions, 1997, # 18, p. 3245 - 3250]
[9]Trincado, Monica; Gruetzmacher, Hansjorg; Vizza, Francesco; Bianchini, Claudio [Chemistry - A European Journal, 2010, vol. 16, # 9, p. 2751 - 2757]
[10]Jiang, Nan; Ragauskas, Arthur J. [Journal of Organic Chemistry, 2007, vol. 72, # 18, p. 7030 - 7033]
[11]Dengel, Andrew C.; El-Hendawy, Ahmed M.; Griffith, William P.; Mostafa, Sahar I.; Williams, David J. [Journal of the Chemical Society, Dalton Transactions, 1992, # 24, p. 3489 - 3496]
[12]Location in patent: experimental part Gorbacheva, Marina; Morozova, Olga; Shumakovich, Galina; Streltsov, Alexander; Shleev, Sergey; Yaropolov, Alexander [Bioorganic Chemistry, 2009, vol. 37, # 1, p. 1 - 5]
[13]Rahimi, Alireza; Azarpira, Ali; Kim, Hoon; Ralph, John; Stahl, Shannon S. [Journal of the American Chemical Society, 2013, vol. 135, # 17, p. 6415 - 6418]
[14]Rahimi, Alireza; Azarpira, Ali; Kim, Hoon; Ralph, John; Stahl, Shannon S. [Journal of the American Chemical Society, 2013, vol. 135, # 17, p. 6415 - 6418]
[15]Rahimi, Alireza; Azarpira, Ali; Kim, Hoon; Ralph, John; Stahl, Shannon S. [Journal of the American Chemical Society, 2013, vol. 135, # 17, p. 6415 - 6418]
[16]Bjorsvik, Hans-Rene; Liguori, Lucia; Minisci, Francesco [Organic Process Research and Development, 2001, vol. 5, # 2, p. 136 - 140]
[17]Napoly, Francois; Jean-Gerard, Ludivine; Goux-Henry, Catherine; Draye, Micheline; Andrioletti, Bruno [European Journal of Organic Chemistry, 2014, vol. 2014, # 4, p. 781 - 787]
[18]Current Patent Assignee: UNIVERSITY OF WISCONSIN SYSTEM; WARF (in: University of Wisconsin) - US2014/235838, 2014, A1
[19]Current Patent Assignee: UNIVERSITY OF WISCONSIN SYSTEM; WARF (in: University of Wisconsin) - US2014/235838, 2014, A1
[20]Current Patent Assignee: UNIVERSITY OF WISCONSIN SYSTEM; WARF (in: University of Wisconsin) - US2014/235838, 2014, A1
[21]Current Patent Assignee: UNIVERSITY OF WISCONSIN SYSTEM; WARF (in: University of Wisconsin) - US2014/235838, 2014, A1
[22]Current Patent Assignee: UNIVERSITY OF WISCONSIN SYSTEM; WARF (in: University of Wisconsin) - US2014/235838, 2014, A1
[23]Current Patent Assignee: UNIVERSITY OF WISCONSIN SYSTEM; WARF (in: University of Wisconsin) - US2014/235838, 2014, A1
[24]Current Patent Assignee: UNIVERSITY OF WISCONSIN SYSTEM; WARF (in: University of Wisconsin) - US2014/235838, 2014, A1
[25]Current Patent Assignee: UNIVERSITY OF WISCONSIN SYSTEM; WARF (in: University of Wisconsin) - US2014/235838, 2014, A1
[26]Current Patent Assignee: UNIVERSITY OF WISCONSIN SYSTEM; WARF (in: University of Wisconsin) - US2014/235838, 2014, A1
[27]Current Patent Assignee: UNIVERSITY OF WISCONSIN SYSTEM; WARF (in: University of Wisconsin) - US2014/235838, 2014, A1
[28]Wu, Xiaochen; Guo, Shouwu; Zhang, Jingyan [Chemical Communications, 2015, vol. 51, # 29, p. 6318 - 6321]
[29]Park, Kwihwan; Jiang, Jing; Yamada, Tsuyoshi; Sajiki, Hironao [Chemical and Pharmaceutical Bulletin, 2021, vol. 69, # 12, p. 1200 - 1205]

10
[ 93-03-8 ]
[ 74-88-4 ]
[ 3840-28-6 ]

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: (3,4-dimethoxyphenyl)methanol With sodium hydride In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Schlenk technique; Stage #2: methyl iodide In tetrahydrofuran at 0 - 20℃; for 3h; Inert atmosphere; Schlenk technique;	1,2-dimethoxy-4-(methoxymethyl)benzene, (1): In a Schleck flask,under N2 atmosphere, 3,4-dimethoxy-benzyl alcohol (3.74 mL, 1 eq,25.7 mmol) is dissolved in dry THF and it is cooled to 0 C. Sodiumhydride 99% (1.0 g, 1 eq, 25.7 mmol) is added portion-wise to the solutionwhich turns to grey. It is left reacting for 30 min at 0 C. Iodomethane(2.09 mL, 1.3 eq, 33.4 mol) is added dropwise to the solution,which is allowed to return to room temperature and it is left reacting for3 h, monitoring by TLC (Hex:AcOEt, 8:2). The reaction is quenched byice-water and ethyl acetate addition. The organic phase is washed withwater, then brine, and it is dried on MgSO4. After salt removal, solutionis taken to dryness by vacuum and the residue dark brown oil is purifiedby column chromatography (Hex:AcOEt, 8:2) to give the product as acolorless oil (yield = 96%). 1H NMR (CDCl3-d, 500 MHz, 25 C), ppm:6.87-6.79 (m, 3H, CHarom), 4.36 (s, 2H, CH2), 3.86 (s, 3H, OCH3), 3.84(s, 3H, OCH3), 3.34 (s, 3H, OCH3). 13C NMR (CDCl3-d, 125 MHz, 25 C),ppm: 149.10, 148.68, 130.84, 120.40, 111.05, 110.92, 74.70, 57.98,56.01, 55.85.
93%	With sodium hydride In tetrahydrofuran at 0 - 20℃; for 3h;
93%	Stage #1: (3,4-dimethoxyphenyl)methanol With sodium hydride In tetrahydrofuran at 0℃; for 0.166667h; Stage #2: methyl iodide In tetrahydrofuran at 20℃; for 3h;	Sodium hydride (95% in oil, 5.22 g, 0.207 mol) was added portion-wise to a solution of 3,4-dimethoxybenzyl alcohol (16) (23 mL, 0.158 mol) in anhydrous THF (150 mL) at 0 0C and the resulting mixture was stirred at 0 0C (10 minutes). To this was added iodomethane (12.86 mL, 0.207 mol) drop-wise and the mixture was allowed to come to ambient temperature and stirred (3 h). The reaction was quenched by the addition of ice and EtOAc, extracted with EtOAc and the combined organic phase was washed with brine and dried (Na2SO4). Evaporation of solvent provided 17 as a colorless residue (27.8 g, 93% yield). 1H NMR (CDCl3): δ 6.83-6.77 (m, 2H), 4.32 (s, 2H), 3.82 (s, 3H), 3.80 (s, 3H), 3.30 (s, 3H); 13C NMR (CDCl3): δ 149.0, 148.5, 130.7, 120.2, 110.9, 110.8, 74.5, 57.8, 55.8, 55.7; FAB-MS m/z 182.1 (M+).

	With sodium hydride In dimethyl sulfoxide
	With sodium hydride In tetrahydrofuran

Reference： [1]Rogolino, Dominga; Naesens, Lieve; Bartoli, Jennifer; Carcelli, Mauro; De Luca, Laura; Pelosi, Giorgio; Stokes, Ryjul W.; Van Berwaer, Ria; Vittorio, Serena; Stevaert, Annelies; Cohen, Seth M. [Bioorganic Chemistry, 2021, vol. 116]
[2]Xue, Zhi Zhao; Semenova, Elena A.; Vu, B. Christie; Maddali, Kasthuraiah; Marchand, Christophe; Hughes, Stephen H.; Pommier, Yves; Burke Jr., Terrence R. [Journal of Medicinal Chemistry, 2008, vol. 51, # 2, p. 251 - 259]
[3]Current Patent Assignee: GOVERNMENT OF THE UNITED STATES - WO2009/26248, 2009, A2 Location in patent: Page/Page column 33; 34
[4]Pincock, J. A.; Wedge, P. J. [Journal of Organic Chemistry, 1994, vol. 59, # 19, p. 5587 - 5595]
[5]Baciocchi, Enrico; Bietti, Massimo; Gerini, Maria Francesca; Manduchi, Laura; Salamone, Michela; Steenken, Steen [Chemistry - A European Journal, 2001, vol. 7, # 7, p. 1408 - 1416]

11
[ 124-38-9 ]
[ 72912-38-0 ]
[ 569-31-3 ]
[ 93-03-8 ]

Reference： [1]Tetrahedron,1995,vol. 51,p. 2489 - 2496

12
[ 72912-38-0 ]
[ 569-31-3 ]
[ 93-03-8 ]

Reference： [1]Tetrahedron,1995,vol. 51,p. 2489 - 2496

13
[ 93-03-8 ]
[ 110451-87-1 ]

Yield	Reaction Conditions	Operation in experiment
100%	With iodine; silver pivalate In chloroform at -5℃; for 1h; Inert atmosphere;
97%	With iodine; mercury(II) oxide In ethanol for 4h; Ambient temperature;
91%	With iodine; silver trifluoroacetate In chloroform at 20℃; for 2h;

64%	With iodine; silver trifluoroacetate In chloroform at 20℃; for 0.5h;
64%	With iodine; silver trifluoroacetate In chloroform at 20℃; for 0.5h;
	With iodine; silver trifluoroacetate In dichloromethane at 20℃;
	With ammonium iodide; oxone In methanol at 20℃; for 8h;
	With iodine; silver trifluoroacetate In chloroform at 22℃; for 2.16667h; Inert atmosphere;

Reference： [1]Arredondo, Vanessa; Roa, Daniel E.; Yan, Songyuan; Liu-Smith, Feng; Van Vranken, David L. [Organic Letters, 2019, vol. 21, # 6, p. 1755 - 1759]
[2]Venter, Daniel P.; Langenhoven, Jan H. [South African Journal of Chemistry, 1996, vol. 49, # 1-2, p. 40 - 46]
[3]Olivera, Roberto; SanMartin, Raul; Dominguez, Esther; Solans, Xabier; Urtiaga, Miren Karmele; Arriortua, Maria Isabel [Journal of Organic Chemistry, 2000, vol. 65, # 20, p. 6398 - 6411]
[4]Ruiz, Javier; Sotomayor, Nuria; Lete, Esther [Organic Letters, 2003, vol. 5, # 7, p. 1115 - 1117]
[5]Ruiz, Javier; Ardeo, Ainhoa; Ignacio, Roberto; Sotomayor, Nuria; Lete, Esther [Tetrahedron, 2005, vol. 61, # 13, p. 3311 - 3324]
[6]Pletnev, Alexandre A.; Larock, Richard C. [Journal of Organic Chemistry, 2002, vol. 67, # 26, p. 9428 - 9438]
[7]Krishna Mohan; Narender; Kulkarni [Tetrahedron Letters, 2004, vol. 45, # 43, p. 8015 - 8018]
[8]Fan, Yi Chiao; Kwon, Ohyun [Organic Letters, 2012, vol. 14, # 13, p. 3264 - 3267]

14
[ 354-38-1 ]
[ 93-03-8 ]
[ 212051-19-9 ]

Reference： [1]Tetrahedron Letters,1998,vol. 39,p. 5565 - 5568

15
[ 42074-68-0 ]
[ 93-03-8 ]
[ 196814-73-0 ]
(S)-2-(2-Benzoyl-phenylamino)-3-[4-(3,4-dimethoxy-benzyloxy)-phenyl]-propionic acid [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,1998,vol. 41,p. 5037 - 5054

16
[ 201230-82-2 ]
[ 72912-38-0 ]
[ 569-31-3 ]
[ 120-14-9 ]
[ 93-03-8 ]

Reference： [1]Journal of Organic Chemistry,1999,vol. 64,p. 6583 - 6596
[2]Journal of Organic Chemistry,1999,vol. 64,p. 6583 - 6596

17
[ 120-14-9 ]
alcoholic KOH-solution [ No CAS ]
[ 2316-26-9 ]
[ 93-07-2 ]
[ 93-03-8 ]

Reference： [1]Journal of the Chemical Society,1926,p. 943,946
Journal of the Chemical Society,1927,p. 2095,2098

18
[ 545-06-2 ]
[ 93-03-8 ]
[ 905589-59-5 ]

Yield	Reaction Conditions	Operation in experiment
97%	Stage #1: (3,4-dimethoxyphenyl)methanol With sodium hydride In tetrahydrofuran Stage #2: trichloroacetonitrile In tetrahydrofuran at 0 - 20℃; for 3h;
90%	With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0℃; Inert atmosphere;
90%	With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0℃; Inert atmosphere;

86%	With 1,8-diazabicyclo[5.4.0]undec-7-ene In hexane at 0℃; for 0.5h;	Synthetic procedure To a suspension of 3,4-dimethoxybenzylalcohol (3a) (175 mg, 1.04 mmol) and Cl3CCN (180 mg, 1.25 mmol) in hexane(3 mL) was added DBU (15.8 mg, 104 μmol) at 0 °C. After the suspension changed to be the solution (actual time = 30min), hexane (3 mL) and saturated aq NH4Cl (5 mL) were added to the reaction mixture. The separated hexane layer waswashed with saturated aq NH4Cl (10 mL). The general drying procedure gave 4a (278 mg, 889 μmol, 86%) as a colorlessoil. The NMR spectra were in good agreement with the literature data of 4a.4
	With sodium hydride In diethyl ether at 0 - 20℃; for 4h;

Reference： [1]Gea, An; Farcy, Nadia; Roque I Rossell, Nuria; Martins, Jose C.; De Clercq, Pierre J.; Madder, Annemieke [European Journal of Organic Chemistry, 2006, # 18, p. 4135 - 4146]
[2]Mahajani, Nivedita S.; Chisholm, John D. [Journal of Organic Chemistry, 2018, vol. 83, # 7, p. 4131 - 4139]
[3]Mahajani, Nivedita S.; Chisholm, John D. [Organic and Biomolecular Chemistry, 2018, vol. 16, # 21, p. 4008 - 4012]
[4]Ikeuchi, Kazutada; Murasawa, Kentaro; Yamada, Hidetoshi [Synlett, 2019, vol. 30, # 11, p. 1308 - 1312]
[5]Dahan; Portnoy [Journal of Organic Chemistry, 2001, vol. 66, # 19, p. 6480 - 6482]

19
[ 93-03-8 ]
[ 76950-76-0 ]

Yield	Reaction Conditions	Operation in experiment
98%	With triethylamine sulfate; potassium iodide for 0.00833333h; Microwave irradiation; Ionic liquid;
92%	With boron trifluoride diethyl etherate; cesium iodide In acetonitrile at 20℃; for 0.333333h;
90%	With sulfuric acid; silica gel; potassium iodide In acetonitrile at 20℃; for 0.75h;

90%	With iodine; triphenylphosphine for 30h; microwave irradiation;
90%	With iodine; triphenylphosphine at 20℃; for 0.0333333h; Ionic liquid;
90%	Stage #1: (3,4-dimethoxyphenyl)methanol With 1H-imidazole; triphenylphosphine In tetrahydrofuran for 0.166667h; Stage #2: With iodine In tetrahydrofuran at 20℃; for 0.5h; Darkness;	6 5.1.6 4-(Iodomethyl)-1,2-dimethoxybenzene (7) Imidazole (0.82 g, 12 mmol) and PPh3 (3.1 g, 12 mmol) were added to a solution of (3,4-dimethoxyphenyl)methanol (1.7 g, 10 mmol) in 25 mL of THF. After stirring for 10 min, iodine (3 g, 12 mmol) was added in darkness and the mixture was stirred at room temperature for 30 min. Solvent was removed in vacuo, and the residue was dissolved in CH2Cl2. The solution was washed with 20 mL NaHSO3 (5%) and brine (2*15 mL), then dried over MgSO4 and concentrated in vacuo. The residue was purified by flash chromatography 1:1 (hexane/Et2O) yielding 757 (2.5 g, 9 mmol, 90% of yield).
89%	With 1-methylimidazole hydrogen sulfate; sodium iodide at 20℃; for 0.0833333h; Grinding; Neat (no solvent); chemoselective reaction;
89%	With iodine In acetonitrile at 120℃; for 0.05h; Microwave irradiation; chemoselective reaction;	4. 2. Typical Procedure for Iodinationof Alcohol General procedure: To a suspension of polymer-bound triphenylphosphine (1.2 mmol) in anhydrous acetonitrile (10 mL) were added iodine (1 mmol) and 1,6-hexanediol diol (1mmol). The reaction mixture was irradiated in microwave reactor at 120 °C for 3 min. The reaction mixture was filtered over a filter paper and washed with chloroform.The filtrate was extracted with aqueous sodium thiosulfate solution and dried with anhydrous sodium sulfate.The reafter, solvent was removed under reduced pressure to obtain 6-iodohexan-1-ol (30) in 93%

Reference： [1]Location in patent: experimental part Hajipour, Abdol R.; Azizi, Ghobad; Ruoho, Arnold E. [Synthetic Communications, 2009, vol. 39, # 2, p. 242 - 250]
[2]Hayat, Safdar; Atta-Ur-Rahman; Khan, Khalid Mohammed; Choudhary, M. Iqbal; Maharvi, Ghulam Murtaza; Zia-Ullah; Bayer, Ernst [Synthetic Communications, 2003, vol. 33, # 14, p. 2531 - 2540]
[3]Hajipour, Abdol R.; Zarei, Amin; Ruoho, Aronold E. [Synthetic Communications, 2006, vol. 36, # 8, p. 1039 - 1050]
[4]Hajipour, Abdol Reza; Falahati, Ali Reza; Ruoho, Arnold E. [Tetrahedron Letters, 2006, vol. 47, # 25, p. 4191 - 4196]
[5]Location in patent: experimental part Hajipour, Abdol Reza; Mostafavi, Majid; Ruoho, Arnold E. [Organic Preparations and Procedures International, 2009, vol. 41, # 1, p. 87 - 91]
[6]López-Sánchez, Cristóbal; Álvarez-Corral, Míriam; Jiménez-González, Leticia; Muñoz-Dorado, Manuel; Rodríguez-García, Ignacio [Tetrahedron, 2013, vol. 69, # 26, p. 5511 - 5516]
[7]Location in patent: experimental part Hajipour, Abdol R.; Rafiee, Fatemeh; Ruoho, Arnold [Synthetic Communications, 2011, vol. 41, # 4, p. 603 - 611]
[8]Das, Diparjun; Chanda, Tridib; Rokhum, Lalthazuala [Acta Chimica Slovenica, 2015, vol. 62, # 4, p. 775 - 783]

20
[ 93-03-8 ]
[ 54370-00-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	With lithium bromide monohydrate; [bis(acetoxy)iodo]benzene; In 2,2,2-trifluoroethanol; at 20℃; for 0.166667h;	General procedure: To a solution of alkoxybenzylalcohol 1 (0.2 mmol) in CF3CH2OH (1 mL) were added LiBr·H2O (0.2 mmol) and PhI(OAc)2 (0.2 mmol) atroom temperature. After completion of the reaction as indicated by TLC monitoring, saturated aq. Na2SO3 wasadded and the mixture was extracted with CH2Cl2. The combined organic layers were washed with brine, driedover anhydrous Na2SO4 and then concentrated in vacuo. The residue was purified by silica gel columnchromatography to afford pure monobrominated compounds 2.

Reference： [1]Synlett,2018,vol. 29,p. 2275 - 2278
[2]Synthetic Communications,2004,vol. 34,p. 2143 - 2152
[3]Organic Letters,2006,vol. 8,p. 487 - 490
[4]Journal of Organic Chemistry,2008,vol. 73,p. 7509 - 7516

21
[ 93-03-8 ]
[ 152563-54-7 ]
[ 916045-27-7 ]
[ 185140-87-8 ]

Yield	Reaction Conditions	Operation in experiment
86%	In acetonitrile at 4℃; for 24h;
86%	In acetonitrile at 4℃; for 24h;	I-e Example (I-e). Synthesis of (R)-3-(3,4-Dimethoxybenzyloxy)-l- triisopropylsiloxy-2-propanol (7); [00331] To a mixture of racemic 2,3-epoxy-l-[(triisopropylsilyl)oxy]propane prepared by literature method1 (2.30g, 10.0 mmol) and 3,4-dimethoxy benzyl alcohol (0.73 mL, 5.0 mmol) in CH3CN (4ml) at 4 0C was added (R,R)-20 (1.6mg, 0.02 mmol) in one portion. [00332] After being stirred 24 h at 4 0C, the reaction mixture was concentrated in vacuo. The residue was purified by silica gel chromatography (hexane : ethyl acetate = 4 : 1) to give (i?)-3-(3,4-dimethoxybenzyloxy)-l-triisopropylsiloxy-2-propanol (7) (1.735 g, 4.35 mmol, 86%) as a colorless oil.[00333] 1H NMR (500 MHz, CDCl3) : δ 6.80 (s, Ar-H, IH), 6.87 (br-d, Ar-H, J= 9.0Hz, IH), 6.82 (d, Ar-H, J= 7.5 Hz, IH), 4.49 (s, Benzylic-H, 2H), 3.88 (s, OMe, 3H), 3.87 (s, OMe, 3H), 3.86 (m, H-2, IH), 3.74 (m, H-I, 2H), 3.53 (m, H-3, 2H), 2.53 (br-s, OH, IH), 1.10 (septet, isopropyl-H, J= 6.5 Hz, 3H), 1.05 (d, isopropyl-Me, J= 6.0 Hz, 18H); 13C NMR (125 MHz, CDCl3) : δ 148.98, 148.62, 130.61, 120.38, 111.06, 110.83, 73.37, 70.79, 70.72, 64.28, 55.90, 55.78, 17.92, 11.85; HRMS (ESI) calcd for C21H42NO5Si [M+ NH4]+ 416.2832, found 416.2836; LRMS (ESI) calcd for C21H42NO5Si [M+ NH4]+ 416.3, found 416.5.

Reference： [1]Adachi, Masaatsu; Zhang, Yi; Leimkuhler, Catherine; Sun, Binyuan; LaTour, John V.; Kahne, Daniel E. [Journal of the American Chemical Society, 2006, vol. 128, # 43, p. 14012 - 14013]
[2]Current Patent Assignee: HARVARD UNIVERSITY - WO2009/46314, 2009, A2 Location in patent: Page/Page column 135-136

22
[ 18698-96-9 ]
[ 93-03-8 ]
3,4-dimethoxybenzyl (2-iodophenyl)acetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃; for 18h;

Reference： [1]Taylor, Stephen R.; Ung, Alison T.; Pyne, Stephen G. [Tetrahedron, 2007, vol. 63, # 45, p. 10889 - 10895]

23
[ 67-56-1 ]
[ 93-03-8 ]
[ 2150-38-1 ]

Yield	Reaction Conditions	Operation in experiment
92%	With Au#Co; oxygen; potassium carbonate; at 80℃; under 750.075 Torr; for 12h;Autoclave;	20 mg of Au-Co composite particle load (0.1 mol%), 13.8 mg K2CO3 (10 mol%), 168.0 mg3,4-dimethoxybenzyl alcohol (1 mmol), 4 mL of methanol was sequentially added to a pressure vessel with a 25 mL glass lining, and after three times of oxygen replacement, the pressure was increased to 0.1 MPa, and the reaction was carried out at 80 C for 12 hours.After cooling to room temperature, slowly depressurize and depressurize, filter the catalyst, and condense the filtrate by steaming.After residue column chromatographyWhite solid productMethyl 3,4-dimethoxybenzoate 176.9 mg, yield 92%.

Reference： [1]Chemical Science,2016,vol. 7,p. 4428 - 4434
[2]Green Chemistry,2014,vol. 16,p. 2164 - 2173
[3]Patent: CN109824513,2019,A .Location in patent: Paragraph 0056; 0057
[4]ACS Catalysis,2019,vol. 9,p. 479 - 484
[5]Journal of the Chinese Chemical Society,2007,vol. 54,p. 1119 - 1122
[6]Catalysis science and technology,2015,vol. 5,p. 1606 - 1622

24
[ 93-03-8 ]
[ 5888-51-7 ]

Reference： [1]Journal of Organic Chemistry,1994,vol. 59,p. 5587 - 5595
[2]Journal of Organic Chemistry,2018,vol. 83,p. 4131 - 4139

25
[ 93-03-8 ]
[ 725-12-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: 95 percent / thionyl chloride / 0 °C 2: 75.5 percent / pyridine / ethanol / 5 h / Heating 3: 95 percent / hydrogen / 5percent palladium on charcoal / ethanol 4: 84 percent / polyphosphoric acid / 3 h / 150 °C

Reference： [1]Paul, D. Brenton [Australian Journal of Chemistry, 1984, vol. 37, # 4, p. 893 - 901]

26
[ 93-03-8 ]
[ 569-31-3 ]

Reference： [1]Journal of Organic Chemistry,1983,vol. 48,p. 3653 - 3657

27
[ 3964-57-6 ]
[ 93-03-8 ]
methyl 4-(3,4-dimethoxybenzyloxy)-3-chlorobenzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	With triphenylphosphine; diethylazodicarboxylate; In tetrahydrofuran; at 0 - 20℃; for 1h;	1A. Preparation of methyl 4-(3,4-dimethoxybenzyloxy)-3-chlorobenzoate A solution of (3,4-dimethoxyphenyl)methanol (6.0 g, 40 mmol) (Aldrich Chemical Co., Milwaukee, Wis.) and <strong>[3964-57-6]methyl 3-chloro-4-hydroxybenzoate</strong> (2.5 g, 13.5 mmol) (Lancaster Synthesis Ltd, Windham, N.H.) in THF (100 mL) was cooled to 0 C. and treated with triphenylphosphine (8.8 g, 33.5 mmol). A solution of diethylazodicarboxylate (5.3 mL, 33.5 mmol) in THF (50 mL) was added dropwise over 30 minutes. After the addition was complete, the reaction was warmed to room temperature and stirred for an additional 30 minutes, and then concentrated to orange oil. The crude reaction was applied directly to a silica column and flushed with hexanes. The desired product was eluted from the column using 25% EtOAc in Hexanes to afford 1A as a light yellow solid (2.5 g, 56%).

Reference： [1]Patent: US2006/135619,2006,A1 .Location in patent: Page/Page column 8

28
[ 2883-98-9 ]
[ 93-03-8 ]
1r-(2,4,5-trimethoxyphenyl)-2t-methyl-5,6-dimethoxyindane [ No CAS ]

Reference： [1]Tetrahedron,2008,vol. 64,p. 4090 - 4102
[2]Magnetic Resonance in Chemistry,2017,vol. 55,p. 619 - 633

29
[ 867033-63-4 ]
[ 7306-46-9 ]
[ 867033-55-4 ]
[ 93-03-8 ]

Yield	Reaction Conditions	Operation in experiment
92%		DMB Ether (+)-2.44:; To a solution of the alcohol (+)-2.S1 (3.04 g, 5.26 mmol) in THF (52 mL) at 0 C. under argon was added 18-crown-6 (316 mL, 1.58 mmol), 35% potassium hydride (1.21 g, 10.5 mmol) and 3,4-dimethoxybenzyl chloride (1.47 g, 7.89 mmol) followed by warming to 65 C. After ten minutes, the reaction mixture was cooled to 0 C. and quenched with saturated aqueous ammonium chloride (70 mL). The resultant mixture was extracted with chloroform (100 mL, 3×) and the combined organic extracts were dried over Na2SO4, filtered and concentrated under reduced pressure. Purification via silica gel chromatography (50% CHCl3/hexanes?100% CHCl3) afforded a mixture of the desired DMB ether (+)-2.44 and 3,4-dimethoxybenzyl alcohol. A second silica gel flash chromatography (10% EtOAc/hexanes) provided pure DMB ether (+)-2.44 (3.52 g, 92%) as a colorless oil. [alpha]D20+29.8 (c 1.8, CHCl3); IR (CHCl3) 2930 (m), 2856 (m), 1516 (s), 1463 (m), 1389 (w), 1266 (s), 1238 (m), 1156 (m), 1112 (s), 1030 (s), 822 (w), 738 (m), 702 (s) cm-1; 1HNMR (500 MHz, CDCl3) delta 7.66 (m, 4H), 7.40 (m, 6H), 6.87 (m, 3H), 6.17 (d, J=1.1 Hz, 1H), 4.57 (d, J=11.2 Hz, 1H), 4.30 (d, J=11.2 Hz, 1H), 3.88 (s, 3H), 3.87 (s, 3H), 3.78 (ddd, J=10.2, 8.6, 4.9 Hz, 1H), 3.72 (ddd, J=10.6, 10.2, 5.4 Hz, 1H), 3.63 (ddd, J=8.2, 4.8, 1.9 Hz, 1H), 3.43 (d, J=10.3 Hz, 1H), 3.17 (dd, J=10.4, 4.7 Hz, 1H), 2.08 (m, 1H), 1.83 (m, 1H), 1.80 (d, J=1.0 Hz, 3H), 1.77 (m, 1H), 1.68 (m, 1H), 1.06 (s, 9H), 0.93 (d, J=6.9 Hz, 3H), 0.80 (d, J=6.5 Hz, 3H); 13CNMR (125 MHz, CDCl3) delta 149.0, 148.6, 146.7, 135.6, 133.9, 133.8, 131.1, 129.6, 129.4, 127.6, 120.2, 111.2, 110.9, 87.5, 83.2, 80.5, 74.9, 69.8, 60.6, 55.9, 55.8, 35.7, 34.2, 33.4, 26.9, 19.2, 19.1, 13.6, 6.0; high resolution mass spectrum (ES+) m/z 751.2320 [(M+Na)+; calcd for C37H49O5SiINa: 751.2292].

Reference： [1]Patent: US7485631,2009,B2 .Location in patent: Page/Page column 48

30
[ 93-03-8 ]
[ 3433-80-5 ]
[ 1151521-22-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: (3,4-dimethoxyphenyl)methanol With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.5h; Stage #2: 1-Bromo-2-bromomethyl-benzene In N,N-dimethyl-formamide at 0℃; for 3h;	4-((2-bromobenzyloxy)methyl)-1,2-dimethoxybenzene. To a stirred solution of 3,4-dimethoxybenzyl alcohol (6.10 mL, 42 mmol) in dry DMF (100 mL) cooled to 0° C., was added 60 wt. % sodium hydride (3.12 g, 78 mmol). After 30 minutes, 2-bromobenzyl bromide (10 g, 40 mmol) was added as a solid. Stirring was continued at 0° C. for 3 hours. The reaction was quenched by slow addition of saturated NH4Cl and extracted with (3×100 mL) EtOAc. The combined organics were washed with brine, dried over MgSO4 and concentrated under vacuum. Column chromatography on silica gel (10-30% ethyl acetate/hexanes) afforded intermediate 1 (14.16 g, 41.9 mmol, 90%). 1H NMR (500 MHz, CHLOROFORM-D) δ ppm 3.88 (d, J=5.19 Hz, 6H) 4.58 (d, J=18.31 Hz, 4H) 6.79-6.87 (m, 1H) 6.89-6.94 (m, 1H) 6.95 (d, J=1.83 Hz, 1H) 7.08-7.17 (m, 1H) 7.31 (t, J=7.17 Hz, 1H) 7.50 (d, J=7.02 Hz, 1H) 7.53 (d, J=7.93 Hz, 1H). Mass spec.: 338.21 (MH)+.

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - US2009/124613, 2009, A1 Location in patent: Page/Page column 15-16

31
[ 93-03-8 ]
[ 90357-51-0 ]
[ 1119117-34-8 ]

Reference： [1]Organic and Biomolecular Chemistry,2009,vol. 7,p. 678 - 686

32
[ 93-03-8 ]
[ 1521-41-1 ]
1,3-bis-(3,4-dimethoxyphenyl)urea [ No CAS ]

Reference： [1]Advanced Synthesis and Catalysis,2010,vol. 352,p. 2588 - 2598

33
[ 93-03-8 ]
[ 1506-76-9 ]

Reference： [1]Journal of the American Chemical Society,2008,vol. 130,p. 14840 - 14852
[2]Journal of the American Chemical Society,2014,vol. 136,p. 7169 - 7185
[3]CrystEngComm,2017,vol. 19,p. 4759 - 4765

34
[ 93-03-8 ]
[ 1521-41-1 ]

Reference： [1]Catalysis Communications,2012,vol. 26,p. 48 - 53
[2]Green Chemistry,2013,vol. 15,p. 1956 - 1961

35
[ 62-53-3 ]
[ 93-03-8 ]
[ 27895-67-6 ]

Yield	Reaction Conditions	Operation in experiment
99%	With potassium <i>tert</i>-butylate; C₁₅H₁₂Cl₂CoN₃ In toluene at 80℃; for 48h; Inert atmosphere;	12 Example 12: Preparation of imine Under the conditions of nitrogen atmosphere, 80 toluene solvent, 1.2 equivalent potassium tert-butoxide, 5% LCoCl2 catalyzed the reaction of aniline with 3,4-dimethoxybenzyl alcohol, reacted for 48 hours to obtain imine, the yield was 99%.
88%	With potassium hydroxide In toluene at 90℃; for 20h;

Reference： [1]Current Patent Assignee: GUANGDONG UNIVERSITY OF PETROCHEMICAL TECHNOLOGY - CN111269141, 2020, A Location in patent: Paragraph 0070-0073
[2]Xu, Jian; Zhuang, Rongqiang; Bao, Lingling; Tang, Guo; Zhao, Yufen [Green Chemistry, 2012, vol. 14, # 9, p. 2384 - 2387]

36
[ 149-30-4 ]
[ 93-03-8 ]
[ 321973-70-0 ]

Yield	Reaction Conditions	Operation in experiment
91%	With N-cetyl-N-(4-sulfobutyl)pyrrolidinium trifluoromethanesulfonate In 1,2-dichloro-ethane at 20℃; for 12h; Schlenk technique;
84%	With 1-Methyl-3-pentylimidazolium hydrogensulfate In acetonitrile at 20℃; for 24h; Green chemistry;	4.1.1. Typical procedure for the benzylation of thiols with benzylic alcohols. General procedure: Thiols (1.0 mmol), benzylic alcohols (1.2 mmol), ionic liquid (0.1 mmol), and CH3CN (2 ml) were added into a flask. Then the mixture was vigorously stirred at room temperature, until thiols were completely consumed as indicated by TLC analysis. After the completion of reaction, the solvent of the resulting mixture was removed with the aid of a rotary evaporator, the residue was directly purified by flash column chromatography with ethyl acetate and petroleum ether (1:6) as eluents to afford pure product.

Reference： [1]Miao, Chengxia; Zhuang, Hongfeng; Wen, Yating; Han, Feng; Yang, Qing-Feng; Yang, Lei; Li, Zhen; Xia, Chungu [European Journal of Organic Chemistry, 2019, vol. 2019, # 19, p. 3012 - 3021]
[2]Chu, Xue-Qiang; Jiang, Ran; Fang, Yi; Gu, Zheng-Yang; Meng, Hua; Wang, Shun-Yi; Ji, Shun-Jun [Tetrahedron, 2013, vol. 69, # 3, p. 1166 - 1174]

37
[ 93-03-8 ]
[ 94687-10-2 ]

Reference： [1]Journal of the American Chemical Society,2013,vol. 135,p. 6415 - 6418
[2]Angewandte Chemie - International Edition,2015,vol. 54,p. 258 - 262
Angew. Chem.,
Angewandte Chemie,
[3]Patent: WO2015/138563,2015,A1

38
[ 106-47-8 ]
[ 93-03-8 ]
[ 13159-76-7 ]

Yield	Reaction Conditions	Operation in experiment
65%	With indium(III) triflate In water at 100℃; for 7h; chemoselective reaction;	4.2 General procedure for the alkylation of indoles, anilines and thiols with enamide General procedure: Amine (1.0mmol), In(OTf)3 (0.1mmol) and anisyl alcohol (1.2mmol) were added into a flask. Then the mixture was vigorously stirred at reflux, until amine was completely consumed as indicated by TLC analysis or 24h. After the completion of reaction, CH2Cl2 (15mL×2) was used to extract the product, the organic layer was dried with anhydrous Na2SO4. Then the solvent was evaporated under the reduced pressure. The residue was purified by flash column chromatography with ethyl acetate and petroleum ether as eluents to afford pure product. This procedure was followed for the synthesis of other N-benzylation amines.

Reference： [1]Yang, Jin-Ming; Jiang, Ran; Wu, Lin; Xu, Xiao-Ping; Wang, Shun-Yi; Ji, Shun-Jun [Tetrahedron, 2013, vol. 69, # 37, p. 7988 - 7994]

39
[ 70-55-3 ]
[ 93-03-8 ]
[ 65588-60-5 ]

Yield	Reaction Conditions	Operation in experiment
90%	With [(η⁵-C₅Me₅)Ir(6,6'-dihydroxy-2,2'-bipyridine)(H₂O)]OTf₂; caesium carbonate In water at 120℃; for 15h; Inert atmosphere; Schlenk technique;
90%	With [(η⁵-C₅Me₅)Ir(6,6'-dihydroxy-2,2'-bipyridine)(H₂O)]OTf₂; caesium carbonate In water at 120℃; for 15h; Schlenk technique;	6 Example 6: N- (3,4- dimethoxybenzyl) -4-methyl-benzenesulfonamide 4-methyl-benzenesulfonamide (171mg, 1mmol), catalyst A (8.3mg, 0.01mmol, 1.0mol%), cesium carbonate (33mg, 0.1mmol, 0.1equiv.), 3,4- dimethoxybenzyl alcohol (202mg, 1.2mmol) and water (1ml) were successively added 25ml Schlenk reaction flask.After the reaction mixture was reacted at 120 15 hours, cooled to room temperature.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: 90%

Reference： [1]Qu, Panpan; Sun, Chunlou; Ma, Juan; Li, Feng [Advanced Synthesis and Catalysis, 2014, vol. 356, # 2-3, p. 447 - 459]
[2]Current Patent Assignee: NANJING UNIVERSITY OF SCIENCE AND TECHNOLOGY - CN104418678, 2016, B Location in patent: Paragraph 0048-0051

40
[ 93-03-8 ]
[ 23702-54-7 ]
[ 1180-60-5 ]

Yield	Reaction Conditions	Operation in experiment
1: 90% 2: 10%	With Tonsil Actisil FF In neat (no solvent) at 85℃; for 0.0333333h; Microwave irradiation;	3.2. Typical Procedure for the Catalytic Reaction under Microwave Conditions General procedure: A mixture of the benzyl alcohols 1a-6a (2 mmol) and Tonsil Actisil FF (20 mg) were reacted in a CEM Discover LabMate in a sealed vessel at 85 °C (100 W and 1 bar of pressure) until disappearance of the starting material. The reaction was conveniently monitored by TLC and the experiments were repeated in various times. Then, the clay was removed by filtration through Celite and washed with ethyl acetate (3 × 5 mL). The combined filtrates were dried on anhydrous Na2SO4, and the solvent was eliminated under reduced pressure. To the benzyl alcohols 1a-3a, the residue was subjected to chromatography on a silica-gel column using n-C6H14/EtOAc as the eluent, affording the compounds 1b-f, 2b-c and 3b-d. To the benzyl alcohols 4a-6a, the presence of benzyl oligomers in the reaction mixtures was determinate by the analysis of GC-EIMS and HRMS spectra, followed the protocol previously described for our group [5,6]. Table 3 shows the elemental composition and high resolution data of oligotoluenes.

Reference： [1]Miranda, Rene; Valencia-Vazquez, Omar; Maya-Vega, Carlos Abel; Nicolas-Vazquez, Ines; Vargas-Rodriguez, Yolanda Marina; Morales-Serna, Jose Antonio; Garcia-Rios, Erendira; Salmon, Manuel [Molecules, 2013, vol. 18, # 10, p. 12820 - 12844]

41
[ 93-03-8 ]
[ 35202-54-1 ]

Reference： [1]Patent: US2014/163220,2014,A1

42
[ 93-03-8 ]
[ 35202-55-2 ]

Reference： [1]Patent: US2014/163220,2014,A1

43
[ 93-03-8 ]
[ 609-36-9 ]
[ 22792-25-2 ]

Yield	Reaction Conditions	Operation in experiment
84%	With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; sodium hydrogencarbonate In toluene at 110℃; for 96h; Inert atmosphere;	General Procedure for the Preparation of 3 General procedure: To a solution of [Cp*IrCl2]2 (0.0025 mmol), amino acid 2(0.65 mmol), and NaHCO3 (0.05 mmol) in toluene (3 mL) under an atmosphere of argon was added alcohol 1 (0.5mmol). The resulting mixture was stirred at 110 °C for a certain period of time. The reaction mixture was cooled tor.t., and H2O (5 mL) was then added. The resulting solution was extracted with EtOAc. Purification on silicon gel afforded the desired products 3.

Reference： [1]Wu, Jiashou; Jiang, Huajiang; Chen, Dingben; Shen, Jianfen; Zhao, Datong; Xiang, Jing; Zhou, Qizhong [Synlett, 2014, vol. 25, # 4, p. 539 - 542]

44
[ 93-03-8 ]
[ 2024-83-1 ]

Yield	Reaction Conditions	Operation in experiment
99%	With ammonia; oxygen In tert-Amyl alcohol; water at 100℃; for 12h; Autoclave; High pressure;
93%	With ammonium hydroxide; copper(l) iodide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; N-Phenylglycine; sodium hydroxide In methanol at 50℃; for 24h; Cooling with ice;	14 General procedure: Reactants used were p-methylbenzyl alcohol (122.03g, 1000mmol, i.e., of formula (I) wherein R is methyl, n = 1, m = 0 , X = C),cuprous iodide (9.50 g of , 50mmol), N- phenylglycine (7.51g, 50mmol), TEMPO ( 7.80g, 50mmol),sodium hydroxide (4.00g, 100mmol), aqueous ammonia (300mL, 25 ~ 28%) ,ethanol, 800mL, in an ice bath under the condition, with oxygen round bottom flask is evacuated of air ventilation 3 times, and then the system was stirred at 25 , 24h, after completion of the reaction, the reaction solution was cooled to room temperature, rotary evaporated to remove the solvent, the residue was washed with water filtered and dried The product was 107.64g, yield 92%. Reactants are methanol and 3,4-dimethoxybenzene (45.65g, 1000mmol, i.e., of formula (I) wherein R is 3,4-dimethoxyphenyl, X = C, n = 1 , m = 0), the same experimental methods and procedures of Example 2, except that: copper iodide (1.90g, 10mmol), N- phenylglycine (1.50g, 10mmol), TEMPO ( 1.56g, 10mmol), potassium sodium hydroxide (7.2g, 180mmol), aqueous ammonia (300mL, 25 ~ 28%) , methanol 800mL, stirred at at 50 24h, to give the final product 136.85g, yield 93%.
88%	Stage #1: (3,4-dimethoxyphenyl)methanol With sodium azide; (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; zinc trifluoromethanesulfonate In acetonitrile at 25℃; Irradiation; Stage #2: With trifluorormethanesulfonic acid In acetonitrile for 1h;

78%	With Iron(III) nitrate nonahydrate; ammonium hydroxide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In acetonitrile at 20℃; for 12h;
68%	With copper(I) oxide; 1,10-Phenanthroline; oxygen; potassium ferrocyanide In dimethyl sulfoxide at 140℃; for 40h; Autoclave;
43 %Chromat.	With copper(ll) sulfate pentahydrate; galactose oxidase from Fusarium sp. variant M<SUB>3‐5</SUB>; ammonium formate; catalase In aq. buffer at 30℃; for 24h; Green chemistry; Enzymatic reaction;
76 %Chromat.	With ammonium hydroxide; oxygen at 50℃; for 12h; Sealed tube; Green chemistry;

Reference： [1]Gates, Bruce C.; Guan, Erjia; Meng, Xiangju; Wang, Chengtao; Wang, Hai; Wang, Liang; Wang, Sai; Xiao, Feng-Shou; Xu, Dongyang; Xu, Hua; Yang, Bo; Zhang, Jian [ACS Catalysis, 2020, vol. 10, # 11, p. 6299 - 6308]
[2]Current Patent Assignee: ZHEJIANG UNIVERSITY OF TECHNOLOGY - CN105294646, 2016, A Location in patent: Paragraph 0043; 0066; 0067
[3]Shee, Maniklal; Shah, Sk. Sheriff; Singh, N. D. Pradeep [Chemistry - A European Journal, 2020, vol. 26, # 62, p. 14070 - 14074]
[4]Dighe, Shashikant U.; Chowdhury, Deepan; Batra, Sanjay [Advanced Synthesis and Catalysis, 2014, vol. 356, # 18, p. 3892 - 3896]
[5]Liu, Wenbo; Tang, Peichen; Zheng, Yi; Ren, Yun-Lai; Tian, Xinzhe; An, Wankai; Zheng, Xianfu; Guo, Yinggang; Shen, Zhenpeng [Chemistry - An Asian Journal, 2021, vol. 16, # 21, p. 3509 - 3513]
[6]Vilím, Jan; Knaus, Tanja; Mutti, Francesco G. [Angewandte Chemie - International Edition, 2018, vol. 57, # 43, p. 14240 - 14244][Angew. Chem., 2018, vol. 130, p. 14436 - 14440,5]
[7]Sun, Kang-Kang; Sun, Jia-Lin; Lu, Guo-Ping; Cai, Chun [Green Chemistry, 2019, vol. 21, # 16, p. 4334 - 4340]

45
[ 135-77-3 ]
[ 93-03-8 ]
[ 54921-95-8 ]

Yield	Reaction Conditions	Operation in experiment
95%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; boron trifluoride diethyl etherate; iodosylbenzene In dichloromethane at 20℃; for 0.5h;	General procedure: General procedure: To the stirred mixture of methoxybenzene (2.0 mmol) and benzylalcohol (1.0 mmol) in DCM (5 mL) were added PhIO (1.2 equiv), TEMPO (0.13 equiv) with BF3.OEt2 (2.0 equiv). The reaction mixture was stirred 30 min at room temperature. The progress of the reaction was monitored by TLC. After completion of the reaction as indicated by TLC, NaHCO3 (3 equiv) was added to the reaction mixture and concentrated in vacuo. The crude product was directly poured into silica gel column chromatography (100-200 mesh) using ethyl acetate: hexane (03:97 to 10:90) as eluent to afford corresponding triarylmethane products. The all obtained products were characterized by 1H NMR, 13C NMR, Mass, HRMS and IR spectral data.

Reference： [1]Babu, B. Madhu; Thakur, Pramod B.; Bangade, Vikas M.; Meshram [Tetrahedron Letters, 2015, vol. 56, # 6, p. 766 - 771]

46
[ 621-23-8 ]
[ 93-03-8 ]
(3,4-dimethoxy-phenyl)-bis-(2,4,6-trimethoxy-phenyl)-methane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; boron trifluoride diethyl etherate; iodosylbenzene In dichloromethane at 20℃; for 0.5h;	General procedure: General procedure: To the stirred mixture of methoxybenzene (2.0 mmol) and benzylalcohol (1.0 mmol) in DCM (5 mL) were added PhIO (1.2 equiv), TEMPO (0.13 equiv) with BF3.OEt2 (2.0 equiv). The reaction mixture was stirred 30 min at room temperature. The progress of the reaction was monitored by TLC. After completion of the reaction as indicated by TLC, NaHCO3 (3 equiv) was added to the reaction mixture and concentrated in vacuo. The crude product was directly poured into silica gel column chromatography (100-200 mesh) using ethyl acetate: hexane (03:97 to 10:90) as eluent to afford corresponding triarylmethane products. The all obtained products were characterized by 1H NMR, 13C NMR, Mass, HRMS and IR spectral data.

Reference： [1]Babu, B. Madhu; Thakur, Pramod B.; Bangade, Vikas M.; Meshram [Tetrahedron Letters, 2015, vol. 56, # 6, p. 766 - 771]

47
[ 93-03-8 ]
[ 151-10-0 ]
C₂₅H₂₈O₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; boron trifluoride diethyl etherate; iodosylbenzene In dichloromethane at 20℃; for 0.5h;	General procedure: General procedure: To the stirred mixture of methoxybenzene (2.0 mmol) and benzylalcohol (1.0 mmol) in DCM (5 mL) were added PhIO (1.2 equiv), TEMPO (0.13 equiv) with BF3.OEt2 (2.0 equiv). The reaction mixture was stirred 30 min at room temperature. The progress of the reaction was monitored by TLC. After completion of the reaction as indicated by TLC, NaHCO3 (3 equiv) was added to the reaction mixture and concentrated in vacuo. The crude product was directly poured into silica gel column chromatography (100-200 mesh) using ethyl acetate: hexane (03:97 to 10:90) as eluent to afford corresponding triarylmethane products. The all obtained products were characterized by 1H NMR, 13C NMR, Mass, HRMS and IR spectral data.

Reference： [1]Babu, B. Madhu; Thakur, Pramod B.; Bangade, Vikas M.; Meshram [Tetrahedron Letters, 2015, vol. 56, # 6, p. 766 - 771]

48
[ 3112-88-7 ]
[ 93-03-8 ]
[ 3892-92-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	With sodium hydride In mineral oil at 135℃; for 28h; Inert atmosphere; Schlenk technique;
85%	With C₁₅H₂₅Cl₂N₃NiO₃; potassium <i>tert</i>-butylate In toluene at 110℃; for 12h; Schlenk technique; Inert atmosphere;
83%	With platinum on carbon; potassium <i>tert</i>-butylate; hydrogen In toluene for 24h; Inert atmosphere; Reflux;

Reference： [1]Yao, Chuan-Zhi; Li, Qiang-Qiang; Wang, Mei-Mei; Ning, Xiao-Shan; Kang, Yan-Biao [Chemical Communications, 2015, vol. 51, # 36, p. 7729 - 7732]
[2]Landge, Vinod G.; Yadav, Vinita; Subaramanian, Murugan; Dangarh, Pragya; Balaraman, Ekambaram [Chemical Communications, 2019, vol. 55, # 43, p. 6130 - 6133]
[3]Hakim Siddiki; Touchy, Abeda Sultana; Kon, Kenichi; Shimizu, Ken-Ichi [Chemistry - A European Journal, 2016, vol. 22, # 17, p. 6111 - 6119]

49
[ 67-71-0 ]
[ 93-03-8 ]
[ 5888-51-7 ]

Reference： [1]Chemistry - A European Journal,2016,vol. 22,p. 6111 - 6119
[2]Angewandte Chemie - International Edition,2014,vol. 53,p. 11092 - 11095
Angew. Chem.,2014,vol. 126,p. 11272 - 11275,4

50
3,4-seco-cycloart-4⁽²⁸⁾,24-diene-3,26-dioic acid [ No CAS ]
[ 538-75-0 ]
[ 93-03-8 ]
C₅₂H₇₈N₂O₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	Stage #1: 3,4-seco-cycloart-4⁽²⁸⁾,24-diene-3,26-dioic acid; dicyclohexyl-carbodiimide In tetrahydrofuran at 0℃; for 0.166667h; Stage #2: (3,4-dimethoxyphenyl)methanol With dmap In tetrahydrofuran at 0 - 20℃; regioselective reaction;	3.2. General procedure for the synthesis of nigranoic acid esters (3a-3l) General procedure: The mixture of nigranoic acid (0.235 g, 0.5mmol) and DCC (0.227 g, 1.1 mmol) was dissolvedin dry THF (5 mL) and stirred under 08C for 10 min, to which the solution of benzyl alcohol(1.1 mmol) and DMAP (0.134 g, 1.1 mmol) in dry THF (5 mL) was added and stirred for 30 minat the same temperature. The reaction mixture was warmed to room temperature and stirredovernight. The solvent was removed by vacuum and the residue was purified by columnchromatography over silica gel (ethyl acetate/petroleum ether 1:4) to afford the targetproduct.

Reference： [1]Huang, Guoli; Feng, Li; Liu, Bo; He, Yi; Li, Yiming; Chen, Yegao [Natural Product Research, 2015, vol. 29, # 17, p. 1650 - 1656]

51
[ 10535-17-8 ]
[ 91-16-7 ]
[ 1835-09-2 ]
[ 22675-96-3 ]
[ 18181-71-0 ]
[ 120-14-9 ]
[ 90-05-1 ]
[ 93-03-8 ]
[ 1131-62-0 ]