1-phenylprop-2-en-1-ol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A second 12 L flask equipped with mechanical stirrer, condensor, and thermocouple was charged with 761.0 g (13.56 mol) KOH (potassium hydroxide), 3.5 L (86.6 mol) of MeOH (methanol), 1.1 L (58.38 mol) of water, and 703 g of vinylbenzyl acetate from the previous step producing a dark red-colored solution. The reaction was heated to reflux and followed by TLC, which indicated that the reaction was complete after 1 hour. The reaction mixture was cooled to room temperature and extracted twice with 4 L of diethyl ether. The ether layer was then washed with three times with 4 L of aqueous sodium chloride, then two times with 4 L of water. The ether layer was dried with MgSO4 (magnesium sulfate) and filtered. Ether was removed from the filtrate under reduced pressure to give a brown oil. (487.0 g, 91% yield) (94% overall). 1H NMR (DMSO-d6): δ 7.35 (m, 4H, aromatic), δ 6.70 (m, 1H, vinyl), δ 5.75 (d, 1H, vinyl), δ 5.25 (d, 1H, vinyl), δ 4.65 (d, 2H, benzyl). A second 12 L flask equipped with mechanical stirrer producing a dark red-colored solution The reaction was heated to reflux extracted twice with 4 L of diethyl ether The ether layer was then washed with three times with 4 L of aqueous sodium chloride The ether layer was dried with MgSO4 (magnesium sulfate) filtered Ether was removed from the filtrate under reduced pressure to give a brown oil

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A second 12 L flask equipped with mechanical stirrer, condensor, and thermocouple was charged with 761.0 g (13.56 mol) KOH (potassium hydroxide), 3.5 L (86.6 mol) of MeOH (methanol), 1.1 L (58.38 mol) of water, and 703 g of vinylbenzyl acetate from the previous step producing a dark red-colored solution. The reaction was heated to reflux and followed by TLC, which indicated that the reaction was complete after 1 hour. The reaction mixture was cooled to room temperature and extracted twice with 4 L of diethyl ether. The ether layer was then washed with three times with 4 L of aqueous sodium chloride, then two times with 4 L of water. The ether layer was dried with MgSO4 (magnesium sulfate) and filtered. Ether was removed from the filtrate under reduced pressure to give a brown oil. (487.0 g, 91% yield) (94% overall). 1H NMR (DMSO-d6): δ 7.35 (m, 4H, aromatic), δ 6.70 (m, 1H, vinyl), δ 5.75 (d, 1H, vinyl), δ 5.25 (d, 1H, vinyl), δ 4.65 (d, 2H, benzyl). A second 12 L flask equipped with mechanical stirrer producing a dark red-colored solution The reaction was heated to reflux extracted twice with 4 L of diethyl ether The ether layer was then washed with three times with 4 L of aqueous sodium chloride The ether layer was dried with MgSO4 (magnesium sulfate) filtered Ether was removed from the filtrate under reduced pressure to give a brown oil

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into 1ι four-necked flask, 57 g (1.425 mol) of sodium hydroxide and 57 ml of deionized water were added under cooling with ice, and a solution of 98.33 g (0.428 mol) of 1,5-dibromopentane and 9.19 g (0.0285 mol) of tetrabutylammonium bromide in 285 mol of toluene was added thereto. The temperature of the solution was set at 50° C., and 70 ml of a toluene solution of 38.25 g (0.285 mol) of vinyl benzyl alcohol (a mixture of m-form and p-form) and 30 mg of DPPH, was dropwise added thereto over a period of one hour. Most of the raw material disappeared during the dropwise addition. This mixture was reacted at 60° C. for 8 hours with vigorous stirring. After the reaction, the organic phase was separated and thoroughly washed with water. This organic phase was dried over magnesium sulfate, and then toluene was distilled off under reduced pressure. The mixture thereby obtained was subjected to vacuum distillation (b.p. 107° to 108° C./40 Pa) in the presence of DPPH to obtain a liquid of a colorless transparent solution. The obtained solution was analyzed by NMR to determine its structure. The amount of 5-bromopentoxymethylstyrene obtained, was 40.8 g, and the yield was 51%. under cooling with ice was set at 50° C. was dropwise added This mixture was reacted at 60° C. for 8 hours with vigorous stirring After the reaction the organic phase was separated thoroughly washed with water This organic phase was dried over magnesium sulfate toluene was distilled off under reduced pressure The mixture thereby obtained was subjected to vacuum distillation (b.p. 107° to 108° C./40 Pa) in the presence of DPPH to obtain a liquid of a colorless transparent solution

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a DMF (0.3 mL) solution of Cu(O-Bu-t) (20 mg, 0.02 mmol) as synthesized according to the method described in the publication Inorg. Chim. Acta, 1981, 20, 2728, (R)-DTBM-SEGPHOS (35 mg, 0.03 mmol) and triethoxysilane fluoride (4.0 μL, 0.02 mmol), benzaldehyde (0.020 mL, 0.20 mmol) and vinyltrimethoxysilane (62 μL, 0.40 mmol) were added at room temperature under an argon atmosphere, the temperature was then raised to 40° C., and the mixture was stirred for 30 minutes. Thereafter, the reaction mixture was allowed to stand for cooling to room temperature, to which was then added tetrabutylammonium fluoride (TBAF) (1M/THF, 0.5 mL), and the mixture was stirred for 10 minutes. After adding water, the mixture was extracted with ethyl acetate, and the resulting organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. After drying, the solvent was distilled off, and the residue was subjected to silica gel column chromatography (ethyl acetate/hexane: 1/9 to 1/4), thereby obtaining desired 1-phenyl-2-propen-1-ol as an (S)-form in a yield of 65% and an optical purity of 94% ee. for cooling to room temperature, to which the mixture was extracted with ethyl acetate the resulting organic layer was washed with saturated brine dried over anhydrous sodium sulfate After drying the solvent was distilled off

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: CuF2.2H2O (3 mg, 0.020 mmol) and (R)-DTBM-SEGPHOS (47 mg. 0.04 mmol) were added to methanol (0.7 mL) under an argon atmosphere, and the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was allowed to stand for cooling to room temperature, and the volatile matter was removed in vacuo. Toluene (0.5 mL) was added to the resulting residue, and the operation for removal of the volatile matter was again carried out twice in vacuo (this catalyst preparation method is designated as “B”; hereinafter the same). The resulting CuF-phosphine complex was dissolved in DMF (1 mL), to which were then added benzaldehyde (67 μL, 0.67 mmol) and vinyltrimethoxysilane (206 μL, 1.34 mmol) at room temperature, and the mixture was stirred at 40° C. for 30 minutes. The reaction mixture was allowed to stand for cooling to room temperature, to which was then added tetrabutylammonium fluoride (TBAF) (1M/THF, 0.5 mL), and the mixture was stirred for 10 minutes. After adding water, the mixture was extracted with ethyl acetate, and the resulting organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. After drying, the solvent was distilled off, and the residue was subjected to silica gel column chromatography (ethyl acetate/hexane: 1/9 to 1/4), thereby obtaining desired 1-phenyl-2-propen-1-ol in a yield of 99%. Its optical purity was measured by HPLC and found to be 94% ee. Furthermore, its absolute configuration was determined in terms of an angle of rotation by comparison with an already reported value. As a result, the product was found to be an (S)-form. the mixture was refluxed for 2 hours the volatile matter was removed in vacuo Toluene (0.5 mL) was added to the resulting residue the operation for removal of the volatile matter this catalyst preparation method for cooling to room temperature, to which the mixture was extracted with ethyl acetate the resulting organic layer was washed with saturated brine dried over anhydrous sodium sulfate After drying the solvent was distilled off

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a DMF (0.2 mL) solution of CuF.3PPh3.2EtOH (10 mg, 0.01 mmol) as synthesized according to the method described in the foregoing publication and dppf (8 mg, 0.014 mmol) (this catalyst preparation method is designated as “A”; hereinafter the same), benzaldehyde (0.020 mL, 0.20 mmol) and vinyltrimethoxysilane (62 μL, 0.40 mmol) were added at room temperature under an argon atmosphere, the temperature was then raised to 60° C., and the mixture was stirred for 3 hours. Thereafter, the reaction mixture was allowed to stand for cooling to room temperature, to which was then added tetrabutylammonium fluoride (TBAF) (1M/THF, 0.5 mL), and the mixture was stirred for 10 minutes. After adding water, the mixture was extracted with ethyl acetate, and the resulting organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. After drying, the solvent was distilled off, and the residue was subjected to silica gel column chromatography (ethyl acetate/hexane: 1/9 to 1/4), thereby obtaining desired 1-phenyl-2-propen-1-ol in a yield of 100%. 3PPh3.2EtOH (10 mg, 0.01 mmol) as synthesized this catalyst preparation method for cooling to room temperature, to which the mixture was extracted with ethyl acetate the resulting organic layer was washed with saturated brine dried over anhydrous sodium sulfate After drying the solvent was distilled off

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a DMF (0.3 mL) solution of Cu(O-Bu-t) (20 mg, 0.02 mmol) as synthesized according to the method described in the publication Inorg. Chim. Acta, 1981, 20, 2728, (R)-DTBM-SEGPHOS (35 mg, 0.03 mmol) and triethoxysilane fluoride (4.0 μL, 0.02 mmol), benzaldehyde (0.020 mL, 0.20 mmol) and vinyltrimethoxysilane (62 μL, 0.40 mmol) were added at room temperature under an argon atmosphere, the temperature was then raised to 40° C., and the mixture was stirred for 30 minutes. Thereafter, the reaction mixture was allowed to stand for cooling to room temperature, to which was then added tetrabutylammonium fluoride (TBAF) (1M/THF, 0.5 mL), and the mixture was stirred for 10 minutes. After adding water, the mixture was extracted with ethyl acetate, and the resulting organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. After drying, the solvent was distilled off, and the residue was subjected to silica gel column chromatography (ethyl acetate/hexane: 1/9 to 1/4), thereby obtaining desired 1-phenyl-2-propen-1-ol as an (S)-form in a yield of 65% and an optical purity of 94% ee. for cooling to room temperature, to which the mixture was extracted with ethyl acetate the resulting organic layer was washed with saturated brine dried over anhydrous sodium sulfate After drying the solvent was distilled off

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: CuF2.2H2O (3 mg, 0.020 mmol) and (R)-DTBM-SEGPHOS (47 mg. 0.04 mmol) were added to methanol (0.7 mL) under an argon atmosphere, and the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was allowed to stand for cooling to room temperature, and the volatile matter was removed in vacuo. Toluene (0.5 mL) was added to the resulting residue, and the operation for removal of the volatile matter was again carried out twice in vacuo (this catalyst preparation method is designated as “B”; hereinafter the same). The resulting CuF-phosphine complex was dissolved in DMF (1 mL), to which were then added benzaldehyde (67 μL, 0.67 mmol) and vinyltrimethoxysilane (206 μL, 1.34 mmol) at room temperature, and the mixture was stirred at 40° C. for 30 minutes. The reaction mixture was allowed to stand for cooling to room temperature, to which was then added tetrabutylammonium fluoride (TBAF) (1M/THF, 0.5 mL), and the mixture was stirred for 10 minutes. After adding water, the mixture was extracted with ethyl acetate, and the resulting organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. After drying, the solvent was distilled off, and the residue was subjected to silica gel column chromatography (ethyl acetate/hexane: 1/9 to 1/4), thereby obtaining desired 1-phenyl-2-propen-1-ol in a yield of 99%. Its optical purity was measured by HPLC and found to be 94% ee. Furthermore, its absolute configuration was determined in terms of an angle of rotation by comparison with an already reported value. As a result, the product was found to be an (S)-form. the mixture was refluxed for 2 hours the volatile matter was removed in vacuo Toluene (0.5 mL) was added to the resulting residue the operation for removal of the volatile matter this catalyst preparation method for cooling to room temperature, to which the mixture was extracted with ethyl acetate the resulting organic layer was washed with saturated brine dried over anhydrous sodium sulfate After drying the solvent was distilled off

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a DMF (0.2 mL) solution of CuF.3PPh3.2EtOH (10 mg, 0.01 mmol) as synthesized according to the method described in the foregoing publication and dppf (8 mg, 0.014 mmol) (this catalyst preparation method is designated as “A”; hereinafter the same), benzaldehyde (0.020 mL, 0.20 mmol) and vinyltrimethoxysilane (62 μL, 0.40 mmol) were added at room temperature under an argon atmosphere, the temperature was then raised to 60° C., and the mixture was stirred for 3 hours. Thereafter, the reaction mixture was allowed to stand for cooling to room temperature, to which was then added tetrabutylammonium fluoride (TBAF) (1M/THF, 0.5 mL), and the mixture was stirred for 10 minutes. After adding water, the mixture was extracted with ethyl acetate, and the resulting organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. After drying, the solvent was distilled off, and the residue was subjected to silica gel column chromatography (ethyl acetate/hexane: 1/9 to 1/4), thereby obtaining desired 1-phenyl-2-propen-1-ol in a yield of 100%. 3PPh3.2EtOH (10 mg, 0.01 mmol) as synthesized this catalyst preparation method for cooling to room temperature, to which the mixture was extracted with ethyl acetate the resulting organic layer was washed with saturated brine dried over anhydrous sodium sulfate After drying the solvent was distilled off

Conditions: temp:0.00; pressure:0.00; stir: