* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With hydrogen; sodium hydroxide In ethanol at 50℃; for 16 h; Autoclave; Inert atmosphere
Example 13Hydrogenation Reaction of Perillaldehyde (S/C=500)Into a stainless steel autoclave equipped with a glass inner tube, [Cu(NO3)(PPh3)2] (11.7 mg, 0.018 mmol) and DPPB (7.7 mg, 0.018 mmol) were introduced. The inside of the autoclave was then replaced with nitrogen. To the autoclave, an ethanolic solution of sodium hydroxide (0.03 M) (6.0 mL, 0.18 mmol) and perillaldehyde (2.02 mL, 9 mmol) were added, and stirring was performed at a hydrogen pressure of 5 MPa at 50° C. for 16 hours. The hydrogen was released with great care, and the conversion was analyzed by GC (>99percent). The contents were concentrated, and then purified by silica gel chromatography. Thus, 1.26 g of the corresponding alcohol was obtained. obtained.
92%
With hydrogen; sodium hydroxide In ethanol at 50℃; for 16 h; Autoclave; Inert atmosphere
(Example 13) Hydrogenation Reaction of Perillaldehyde (S/C=500) Into a stainless steel autoclave equipped with a glass inner tube, [Cu(NO3)(PPh3)2] (11.7mg, 0.018 mmol) and DPPB (7.7 mg, 0.018 mmol) were introduced. The inside of the autoclave was then replaced with nitrogen. To the autoclave, an ethanolic solution of sodium hydroxide (0.03 M) (6.0 mL, 0.18 mmol) and perillaldehyde (2.02 mL, 9 mmol) were added, and stirring was performed at a hydrogen pressure of 5 MPa at 50°C for 16 hours. The hydrogen was released with great care, and the conversion was analyzed by GC (>99percent). The contents were concentrated, and then purified by silica gel chromatography. Thus, 1.26 g of the corresponding alcohol was obtained. Isolated yield: 92percent, 1d/2d = 52/1
35%
With 1,1'-bis-(diphenylphosphino)ferrocene; silver(I) hexafluorophosphate; tripropylsilane; N-ethyl-N,N-diisopropylamine In water at 100℃; for 24 h;
General procedure: Degassed CH2Cl2 (0.25 mL) was added to a microwave tube containing the ligand dppf (8.3 mg, 0.015 mmol) and AgPF6 (2.5 mg, 0.01 mmol) under argon. The resulting suspension was stirred at r.t., until a clear, colorless solution was obtained; then the solvent was removed under high vacuum. Benzaldehyde (1a; 20.3 μL, 0.2 mmol), tripropylsilane (2a;125 μL, 0.6 mmol), DIPEA (6.9 μL, 0.04 mmol), and H2O(0.5 mL) were subsequently added. The reaction mixture was stirred for 24 h at 100 °C, then cooled to r.t. and extracted with CH2Cl2 (3 × 10 mL). The combined organicphase was concentrated and purified by flash column chromatography on silica gel (hexane–EtOAc, 20:1) to give the desired product 3a as a colorless oil (19.5 mg, 90percent).
Reference：
[1] Tetrahedron Letters, 1993, vol. 34, # 2, p. 257 - 260
[2] Chemistry - A European Journal, 2017, vol. 23, # 35, p. 8473 - 8481
[3] Synlett, 2009, # 8, p. 1295 - 1298
[4] Patent: US2011/201819, 2011, A1, . Location in patent: Page/Page column 10
[5] Patent: EP2377841, 2011, A1, . Location in patent: Page/Page column 13-14
[6] Chemistry - A European Journal, 2013, vol. 19, # 17, p. 5255 - 5258
[7] Journal of the American Chemical Society, 2016, vol. 138, # 28, p. 8809 - 8814
[8] Tetrahedron, 1990, vol. 46, # 9, p. 3315 - 3320
[9] Tetrahedron Letters, 1990, vol. 31, # 8, p. 1185 - 1186
[10] Synlett, 2013, vol. 24, # 16, p. 2049 - 2056
[11] Phytochemistry (Elsevier), 1986, vol. 25, # 12, p. 2769 - 2776
[12] Patent: US2011/201820, 2011, A1, . Location in patent: Page/Page column 8
[13] Patent: EP2374783, 2011, A1, . Location in patent: Page/Page column 11
[14] Chemistry Letters, 2013, vol. 42, # 6, p. 660 - 662
[15] Catalysis Science and Technology, 2015, vol. 5, # 6, p. 3108 - 3112
[16] Organic Letters, 2018, vol. 20, # 16, p. 5040 - 5043
2
[ 2111-75-3 ]
[ 18479-64-6 ]
[ 536-59-4 ]
Reference：
[1] Chemical Communications, 2013, vol. 49, # 63, p. 7034 - 7036
[2] Patent: JP2015/48349, 2015, A, . Location in patent: Paragraph 0074-0076
3
[ 6931-54-0 ]
[ 536-59-4 ]
Reference：
[1] Tetrahedron, 2009, vol. 65, # 52, p. 10837 - 10841
[2] Patent: US3993604, 1976, A,
[3] Research on Chemical Intermediates, 2012, vol. 38, # 8, p. 2075 - 2084
[4] Research on Chemical Intermediates, 2012, vol. 38, # 8, p. 2075 - 2084
4
[ 6931-54-0 ]
[ 4764-14-1 ]
[ 536-59-4 ]
Reference：
[1] Applied Catalysis A: General, 2010, vol. 380, # 1-2, p. 165 - 171
Reference：
[1] Journal of Physical Chemistry A, 2017, vol. 121, # 48, p. 9297 - 9305
15
[ 6931-54-0 ]
[ 5502-74-9 ]
[ 536-59-4 ]
Reference：
[1] Journal of Physical Chemistry A, 2017, vol. 121, # 48, p. 9297 - 9305
16
[ 177698-19-0 ]
[ 6931-54-0 ]
[ 24903-95-5 ]
[ 5502-74-9 ]
[ 536-59-4 ]
[ 515-00-4 ]
Reference：
[1] Advanced Synthesis and Catalysis, 2010, vol. 352, # 10, p. 1771 - 1778
17
[ 536-59-4 ]
[ 23635-14-5 ]
[ 18031-40-8 ]
Yield
Reaction Conditions
Operation in experiment
65%
With tert-butyl 1-hydroxy-2-methyl-6-trifluoromethyl-1H-indole-3-carboxylate; oxygen; copper(l) chloride In N,N-dimethyl-formamide at 50℃; for 24 h;
General procedure: To a 10 mL Schlenk tube, NHI-1 (0.2 mmol, 63 mg) and CuCl (0.2 mmol, 19.6 mg) and DMF (2 mL) were added and stirred at 50 °C for about 30 min to form a dark red solution. Alcohol 11 (2 mmol) was added, the mixture was left to stir at 50 °C under an oxygen balloon (1 atm). The reaction progress was monitored by TLC or GC. After completion, the mixture was allowed to cool to room temperature, quenched with 1M HCl and diluted with H2O (50 mL), extracted with EtOAc (EA) (10 mL .x. 3), the combined organic layer was washed with brine and dried over MgSO4, the crude was purified by flash column chromatography (EtOAc : hexane = 1 : 10 to 1: 3) to afford ketone or aldehyde 12.
Reference：
[1] Tetrahedron Letters, 2012, vol. 53, # 8, p. 986 - 990
[2] Green Chemistry, 2012, vol. 14, # 8, p. 2158 - 2161
18
[ 536-59-4 ]
[ 18031-40-8 ]
Yield
Reaction Conditions
Operation in experiment
20 %Chromat.
With tert.-butylhydroperoxide; manganese(IV) oxide In decane; toluene; acetonitrile at 20℃; for 24 h;
General procedure: The alcohol (1.2mmol) of interest was dissolved in a mixture of acetonitrile (3ml) and toluene (1ml) for the experiments with TBHP/decane (or in 4ml of acetonitrile for the experiments with TBHP/H2O) and the desired amount of MnO2 (see Tables) was added to the solution. Then tert-butyl hydroperoxide (TBHP, as a 5.3M solution in decane, 453μL, 2.4mmol) was added to the reaction mixture, which was set at the desired reaction temperature with magnetic stirring in air. Aliquots (0.2ml) were withdrawn at different time intervals, diluted with 1ml of diethyl ether and filtered through a Pasteur pipette filled up with silica to eliminate the residual MnO2. The silica was washed with 2ml of diethyl ether. The resulting organic phase was analyzed by gas chromatography using diethyleneglycol dibutyl ether as an external standard.
Reference：
[1] Synlett, 2002, # 4, p. 616 - 618
[2] Chemistry - A European Journal, 2009, vol. 15, # 41, p. 10901 - 10911
[3] Australian Journal of Chemistry, 1996, vol. 49, # 7, p. 741 - 749
[4] Angewandte Chemie - International Edition, 2001, vol. 40, # 23, p. 4393 - 4394
[5] Tetrahedron, 2010, vol. 66, # 51, p. 9688 - 9693
[6] ACS Catalysis, 2015, vol. 5, # 2, p. 1313 - 1317
[7] Journal of Medicinal Chemistry, 2014, vol. 57, # 17, p. 7478 - 7484
[8] Organic Letters, 2014, vol. 16, # 19, p. 5224 - 5227
[9] New Journal of Chemistry, 2017, vol. 41, # 6, p. 2372 - 2377
[10] Tetrahedron, 1993, vol. 49, # 3, p. 619 - 638
[11] Chemische Berichte, 1981, vol. <193> 114, # 1, p. 118 - 131
[12] Bulletin de la Societe Chimique de France, 1958, p. 393
[13] Journal of Organic Chemistry, 1997, vol. 62, # 17, p. 5664 - 5665
[14] Organic and Biomolecular Chemistry, 2012, vol. 10, # 9, p. 1746 - 1749
[15] Journal of Organic Chemistry, 2014, vol. 79, # 22, p. 11091 - 11100
[16] Comptes Rendus Chimie, 2016, vol. 19, # 5, p. 566 - 570
[17] Planta Medica, 2016, vol. 82, # 15, p. 1346 - 1350
Stage #1: perillaldehyde With [Ru(NNSEt)(PPh3)Cl2]; potassium <i>tert</i>-butylate In isopropyl alcohol Autoclave; Inert atmosphere;
Stage #2: With hydrogen In isopropyl alcohol at 80℃; for 1h;
92%
With [Cu(PPh3)2NO3]; hydrogen; 1,4-di(diphenylphosphino)-butane; sodium hydroxide In ethanol at 50℃; for 16h; Autoclave; Inert atmosphere; chemoselective reaction;
92%
With hydrogen; sodium hydroxide In ethanol at 50℃; for 16h; Autoclave; Inert atmosphere;
13
Example 13Hydrogenation Reaction of Perillaldehyde (S/C=500)Into a stainless steel autoclave equipped with a glass inner tube, [Cu(NO3)(PPh3)2] (11.7 mg, 0.018 mmol) and DPPB (7.7 mg, 0.018 mmol) were introduced. The inside of the autoclave was then replaced with nitrogen. To the autoclave, an ethanolic solution of sodium hydroxide (0.03 M) (6.0 mL, 0.18 mmol) and perillaldehyde (2.02 mL, 9 mmol) were added, and stirring was performed at a hydrogen pressure of 5 MPa at 50° C. for 16 hours. The hydrogen was released with great care, and the conversion was analyzed by GC (>99%). The contents were concentrated, and then purified by silica gel chromatography. Thus, 1.26 g of the corresponding alcohol was obtained. obtained.
92%
With hydrogen; sodium hydroxide In ethanol at 50℃; for 16h; Autoclave; Inert atmosphere;
13
(Example 13) Hydrogenation Reaction of Perillaldehyde (S/C=500) Into a stainless steel autoclave equipped with a glass inner tube, [Cu(NO3)(PPh3)2] (11.7mg, 0.018 mmol) and DPPB (7.7 mg, 0.018 mmol) were introduced. The inside of the autoclave was then replaced with nitrogen. To the autoclave, an ethanolic solution of sodium hydroxide (0.03 M) (6.0 mL, 0.18 mmol) and perillaldehyde (2.02 mL, 9 mmol) were added, and stirring was performed at a hydrogen pressure of 5 MPa at 50°C for 16 hours. The hydrogen was released with great care, and the conversion was analyzed by GC (>99%). The contents were concentrated, and then purified by silica gel chromatography. Thus, 1.26 g of the corresponding alcohol was obtained. Isolated yield: 92%, 1d/2d = 52/1
91%
With [Cp*Ir(2,2'-bpyO)(OH)][Na]; hydrogen In water at 30℃; for 12h; Green chemistry;
4.1. General procedure for catalytic hydrogenation of ketones,aldehydes or unsaturated aldehydes
General procedure: To an oven-dried 5 mL round-bottom flask were added ketonesor aldehydes or unsaturated aldehydes (1 mmol), cat. 6 (5.5 mg,1 mol %) and H2O (1 mL). Next, vacuum was applied to the flask followedby filling with H2 gas and keeping the flask attached to a balloonfilled with H2 gas. The mixture was heated at 30 °C for 12 h.After completion of the reaction, the mixture was extracted withethyl acetate (5 mL x 3). Then, the ethyl acetate layers were combined, dried with anhydrous sodium sulfate, filtered, and concentratedby evaporation under reduced pressure. The alcohols wereisolated and purified by filtering a hexanes/ethyl acetate (8:1)solution of the crude product through a pad of silica gel. Thenthe solvent was removed under reduced pressure to afford the correspondingproducts. The purity of alcohol products was assessedusing 1H NMR spectroscopy.
91%
With [Cp*Ir(2,2'-bpyO)(OH)][Na]; hydrogen In water at 30℃; for 12h;
12 This method:
Perillaldehyde (150 mg, 1.0 mmol) and metal iridium complex [Cp*Ir(2,2'-bpyO)(OH)][Na] (4.6 mg, 0.01 mmol, 1 mol%) add water (1 mL) to a 5 mL round-bottom flask one by one, and replace the air in the round-bottom flask with hydrogen gas. During the whole reaction process, the pressure of hydrogen in the system was maintained at 1 standard atmosphere, and the reaction mixture was reacted at 30° C. in a hydrogen atmosphere for 12 h. After the reaction, the solvent was removed by rotary evaporation, and then column chromatography (developing solvent: petroleum ether: ethyl acetate volume ratio = 10:1) was used to obtain the pure target compound with a yield of 91%.
90%
With hydrogen In tetrahydrofuran at 150℃; for 18h; Autoclave; chemoselective reaction;
89%
With MnBr(CO)2[NH(CH2CH2P(iPr)2)2]; hydrogen; sodium t-butanolate In toluene at 100℃; for 24h; Autoclave; chemoselective reaction;
80%
In water; N,N-dimethyl-formamide for 5h; Ambient temperature;
80%
With water; antimony chloride; zinc In N,N-dimethyl-formamide for 5h; Ambient temperature;
35%
With 1,1'-bis-(diphenylphosphino)ferrocene; silver(I) hexafluorophosphate; tripropylsilane; N-ethyl-N,N-diisopropylamine In water at 100℃; for 24h;
Typical Procedure for Reduction of Aldehydes withSilanes in Water
General procedure: Degassed CH2Cl2 (0.25 mL) was added to a microwave tube containing the ligand dppf (8.3 mg, 0.015 mmol) and AgPF6 (2.5 mg, 0.01 mmol) under argon. The resulting suspension was stirred at r.t., until a clear, colorless solution was obtained; then the solvent was removed under high vacuum. Benzaldehyde (1a; 20.3 μL, 0.2 mmol), tripropylsilane (2a;125 μL, 0.6 mmol), DIPEA (6.9 μL, 0.04 mmol), and H2O(0.5 mL) were subsequently added. The reaction mixture was stirred for 24 h at 100 °C, then cooled to r.t. and extracted with CH2Cl2 (3 × 10 mL). The combined organicphase was concentrated and purified by flash column chromatography on silica gel (hexane-EtOAc, 20:1) to give the desired product 3a as a colorless oil (19.5 mg, 90%).
With lithium aluminium tetrahydride
With hydrogen; triphenylphosphine; sodium hydroxide In ethanol at 50℃; for 16h; Inert atmosphere;
9
Into a stainless steel autoclave equipped with a glass inner tube, Cu(NO3)(PPh3)2 (11.7 mg, 0.018 mmol) and triphenylphosphine (28.3 mg, 0.108 mmol) were introduced. The inside of the autoclave was then replaced with nitrogen. To the autoclave, an ethanolic solution of sodium hydroxide (0.03 M) (6.0 mL, 0.18 mmol) and perillaldehyde (1.40 mL, 9 mmol) were added, and stirring was performed at a hydrogen pressure of 5 MPa at 50° C. for 16 hours. The hydrogen was released with great care, and the conversion was analyzed by GC. The conversion was 52%.
With hydrogen; sodium hydroxide In ethanol at 50℃; for 16h; Autoclave;
9
(Example 9) Hydrogenation Reaction of Perillaldehyde; Into a stainless steel autoclave equipped with a glass inner tube, Cu(NO3)(PPh3)2 (11.7 mg, 0.018 mmol) and triphenylphosphine (28.3 mg, 0.108 mmol) were introduced. The inside of the autoclave was then replaced with nitrogen. To the autoclave, an ethanolic solution of sodium hydroxide (0.03 M) (6.0 mL, 0.18 mmol) and perillaldehyde (1.40 mL, 9 mmol) were added, and stirring was performed at a hydrogen pressure of 5 MPa at 50°C for 16 hours. The hydrogen was released with great care, and the conversion was analyzed by GC. The conversion was 52%.
98 %Chromat.
With hydrogen; caesium carbonate In tetrahydrofuran at 110℃; for 18h; Autoclave; chemoselective reaction;
With hydrogen In ethanol at 70℃; for 1h; chemoselective reaction;
With sodium tetrahydroborate In ethanol at 0℃; for 2h;
77 %
With potassium phosphate; hydrogen; C18H25BrMnN4O2P In methanol at 27℃;
With oxygen In 1,3,5-trimethyl-benzene at 60℃; for 4h;
8.17 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.
90%
With Iron(III) nitrate nonahydrate; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen; sodium chloride In 1,2-dichloro-ethane at 20℃; for 9h;
90%
With tert.-butylhydroperoxide; oxygen In decane; toluene at 80℃; Schlenk technique;
87%
With sodium hydroxide; dipotassium peroxodisulfate In dichloromethane; water for 24h; Ambient temperature;
85%
With potassium carbonate In n-heptane at 80℃; for 24h;
S4. Procedure for the synthesis of aldehydes and ketones
General procedure: A magnetic stir bar, 0.5 mmol alcohol and 3 mL n-heptane solvent were added to 20 mL glass tube. Then, 35mg catalyst and 10 mol% of K2CO3 were added. The glass tube containing reaction mixture was f itted withseptum and connected to a balloon containing one bar of air. Then the glass tube was placed into a preheatedaluminum block at 85°C. Temperature inside the reaction tube was measured to be 80 oC and this temperaturehas been taken as the reaction temperature. The reaction was allowed to progress under continuous stirringfor the required time at 80 °C. Af ter completion of the reaction, the glass tube was cooled down to roomtemperature. Afterwards, the catalyst was f iltered-off and washed with ethyl acetate. The solvent f rom thef iltrate containing the reaction products was removed in vacuum and the corresponding aldehyde/ketone waspurif ied by column chromatography. All products were analyzed by GC-MS and NMR spectroscopy analysis.In the case of yields determined the by GC, 100 μL n-hexadecane was added to the reaction vial containingthe products and diluted with ethyl acetate. Then, the reaction mixture containing catalyst and products wasf iltered through a plug of silica and the filtrate containing product was analyzed by GC.
80%
Stage #1: perillol With C24H20B(1-)*C5H12NO2(1+)*C5H11NO2 In acetonitrile at 20℃; for 0.166667h;
Stage #2: With tetrapropylammonium perruthennate In acetonitrile at 20℃;
75%
With tetrapropylammonium perruthennate; N,N,N′,N′-tetramethylethylenediamine dioxide In dichloromethane at 20℃; for 4h; Molecular sieve; Inert atmosphere;
63%
With oxygen; copper(II) oxide In cyclohexane at 90℃; for 2h;
Synthesis of Perillaldehyde 6
In a typical procedure, perillyl alcohol 5 (4 mmol, 1 eq.), Eco-NaMnOx-Ps (8 mmol, 2eq. of Mn) and CuO (16 mmol, 4 eq.) were introduced in a flask containing cyclohexane(20 mL) under reflux and an O2 atmosphere for 2 h. The O2 atmosphere was ensured byusing a bottle of dioxygene with an exit pressure of 0.1 mbar. The mixture was filteredand washed three times with ethyl acetate. The filtrate was collected, and its solvent wasevaporated. Perillaldehyde was purified on a silica column using an eluant of 10% ethylacetate and 90% of cyclohexane.1H NMR (400 MHz, acetone_d6): (ppm): 1.40-1.47 (m, 1H, H3b); 1.76 (s, 3H, H10);1.93-1.88 (m, 1H, H4); 2.11-2.14 (m, 1H, H3a); 2.29-2.23 (m, 2H, H2); 2.40-2.32 (m, 1H,H5b); 2.53-2.44 (m, 1H, H5a); 4.76-4.74 (m, 1H, H9b); 4.78-4.76 (m, 1H, H9a); 6.92 (m, 1H,H6); 9.44 (s, 1H, H7).13C NMR (100 MHz, acetone_d6): (ppm): 20 (C10); 22 (C2); 27 (C3); 32 (C5); 41 (C4);110 (C9); 142 (C1); 149 (C8); 151 (C6); 194 (C7).
96 % Turnov.
With 2,4,6-trimethylphenyl bromide; potassium carbonate In 1,2-dimethoxyethane at 85℃; for 12h;
With oxygen In toluene at 100℃; for 5h; chemoselective reaction;
2.4. Catalytic oxidation experiments
General procedure: The reactions were carried out in a stainless steel reactor equipped with a magnetic stirrer. In a typical run, a mixture of the substrate (1.0 mmol), toluene (5 mL), and the catalyst (0.02-0.2 g; ca. 0.45-4.5 wt.%; Ru: 0.28-2.80 mol%) was transferred in the reactor. The reactor was pressurized with oxygen to the total pressure of 10 atm and placed in an oil bath; then, the solution was intensively stirred at 80-120 °C for the reported time. The reactions were followed by gas chromatography (GC) (Shimadzu 17 instrument, Carbowax 20 M capillary column). To take the aliquots for the GC analysis at appropriate time intervals, stirring was stopped and the catalyst was quickly settled by the application of an external permanent magnet. The structures of the products were confirmed by GC/MS (Shimadzu QP2010-PLUS instrument, 70 eV).
48 %Chromat.
With 6-(N-phenylbenzimidazoyl)-2-pyridinecarboxylic acid; dihydrogen peroxide; sodium carbonate; iron(II) chloride In dichloromethane at 20℃; for 0.5h; chemoselective reaction;
With oxygen In methanol at 110℃; for 7h; Stainless steel reactor; chemoselective reaction;
2.3. Catalytic oxidation experiments
General procedure:The reactions were carried out in a stainless steel reactor equipped with a magnetic stirrer. In a typical run, a mixture of the substrate (0.4-1.2 mmol), solvent (if any) (2 mL), and the catalyst (10-40 mg; ca. 0.6-2.4 wt.%; Au: 0.01-0.75 mol%) was transferred in the reactor. The reactor was pressurized with oxygen to the total pressure of 10 atm and placed in an oil bath; then, the solution was intensively stirred at 80-130 °C for the reported time. The reactions were followed by gas chromatography (GC) (Shimadzu 17 instrument, Carbowax 20 M capillary column). At appropriate time intervals, stirring was stopped and after catalyst settling aliquots were taken and analyzed by GC. To ensure correct GC results in solvent-free reactions and in those with high initial substrate concentrations, the aliquots were diluted with methanol before the analysis. The structures of the products were confirmed by GC/MS (Shimadzu QP2010-PLUS instrument, 70 eV).
With Dess-Martin periodane In dichloromethane at 20℃; for 1h;
With oxygen In toluene at 80℃; for 3h; chemoselective reaction;
98 %Chromat.
With sodium hypochlorite; (Et4N)2[FeIII(Cl)(biuret-TAML)] In aq. phosphate buffer; acetonitrile at 20℃; for 5h; chemoselective reaction;
3.1.1. Procedure for reactions at pH 7
General procedure: To a reaction vial containing a magnetic stir bar, unsubstituted Fe-bTAML catalyst, 1 (0.2-0.8mM, 0.5-2mol %), substrate (40mM, 0.04mmol, 1.0equiv.) and pH 7 phosphate buffer (100mM, 300μL aqueous solution) in 700μL acetonitrile were added. An aqueous solution of sodium hypochlorite (2equiv.) was added via syringe pump with continuous stirring over a period of 2-6h at room temperature. The reaction was monitored by TLC and GC. After completion of the reaction, the solvent (CH3CN) was removed under reduced pressure. Saturated aqueous solution of sodium bicarbonate was added to the residual portion and extracted with dichloromethane (2times). The organic part was dried with anhydrous sodium sulphate, analysed by GC-MS to estimate the product GC yield.
With tert-butyl 1-hydroxy-2-methyl-6-trifluoromethyl-1H-indole-3-carboxylate; oxygen; copper(l) chloride; In N,N-dimethyl-formamide; at 50℃; under 760.051 Torr; for 24h;
General procedure: To a 10 mL Schlenk tube, NHI-1 (0.2 mmol, 63 mg) and CuCl (0.2 mmol, 19.6 mg) and DMF (2 mL) were added and stirred at 50 C for about 30 min to form a dark red solution. Alcohol 11 (2 mmol) was added, the mixture was left to stir at 50 C under an oxygen balloon (1 atm). The reaction progress was monitored by TLC or GC. After completion, the mixture was allowed to cool to room temperature, quenched with 1M HCl and diluted with H2O (50 mL), extracted with EtOAc (EA) (10 mL × 3), the combined organic layer was washed with brine and dried over MgSO4, the crude was purified by flash column chromatography (EtOAc : hexane = 1 : 10 to 1: 3) to afford ketone or aldehyde 12.
A solution of isoperillyl alcohol (0.17 g, 1.12 mmol) in 1,2-dichloroethane (5 mL) will be added over a period of 10 min. The reaction mixture will be allowed to warm to room temperature and stirred for 12 h. 1,2-Dichloroethane will be concentrated under vacuum to give a residue which will be triturated with hexanes. The resulting pale yellow solid will be filtered and washed with hexanes. The product iso-POH carbamate may be partially or fully deuterated. For example, one or more of the H atoms may be deuterium.
With cis-Octadecenoic acid; palladium on activated charcoal In cyclohexane at 110℃; for 2h;
1
To a 100ml reaction vessel, 10ml perilla alcohol was added, 20ml of cyclohexane was used as the reaction solvent , added 0.8 g of palladium / Carbon catalyst, 4g oleic aid degreasing agent. Stirring was done in the autoclave, the reaction temperature was controlled at 110°C , the reaction ended after 2 hours to give the product which was purified by distillation or rectification cumin alcohol. Perilla alcohol conversion was greater than 99%, cumin Alcohol yield of 95%
91%
With 5 weight% palladium(0) nanoparticles supported on mesoporous natural phosphate In neat (no solvent) for 24h; Reflux;
(3-methyl 4-oxo-3,4-dihydroimidazo[5,1-d][1,2,3,5]tetrazine-8-carbonyl)carbamic acid-4-isopropenyl cyclohex-1-enylmethyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
89%
Oxalyl chloride (0.13 grams, 1.0 mmol) was added slowly to a mixture of <strong>[85622-93-1]temozolomide</strong> (OChem Incorporation, 0.1 grams, 0.5 mmol) in 1,2-dichloroethane (10 mL) over a period of 2 minutes while maintaining the temperature at 10 C under N2. The reaction mixture was allowed to warm to room temperature and then heated to reflux for 3 hours. The excess of oxalyl chloride and 1,2-dichloroethane were removed by concentration under vacuum. The resulting residue was re-dissolved in 1,2-dichlorethane (15 mL) and the reaction mixture was cooled to 10 C under N2. A solution of perillyl alcohol (0.086 grams, 0.56 mmol) in 1,2-dichloroethane (3 mL) was added over a period of 5 minutes. The reaction mixture was allowed to warm to room temperature and stirred for 14 hours. 1,2-dichloroethane was concentrated under vacuum to give a residue, which was triturated with hexanes. The resulting yellow solid was filtered and washed with hexanes. Weight: 170 mg; Yield: 89%. ^ NMR (400 MHz, CDC13): delta 1.4-2.2 (m, 10H), 4.06 (s, 3H), 4.6-4.8 (m, 4H), 5.88 (br s, IH), 8.42 (s, IH), 9.31 (br s, IH); MS, no molecular ion peak was observed, m/e: 314 (100%), 286.5 (17%), 136 (12%).
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