1-phenylbut-3-en-1-ol

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

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 2-bromo-1-octene (1.25 g, 6.6 mmol, 1.1 equiv) in Et2O (7 mL) was added dropwise t-BuLi (1.5 M, 8.8 mL, 13.2 mmol, 2.2 equiv) under a N2 atmosphere at −78° C. (internal). The pale-yellow, cloudy mixture was stirred for 1 h at −78° C. (internal). The mixture was then added to a solution of dichlorodimethylsilane (1.82 mL, 15.0 mmol, 2.5 equiv) in Et2O (10 mL) by cannula at −78° C. (internal). The mixture was allowed to warm to room temperature and was stirred for 2 h whereupon a white solid precipitated. After removal of solvent and excess dichlorodimethylsilane under reduced pressure, hexane (50 mL) was added and the solids were removed by Schlenk filtration. After removal of the solvent, the residue was dissolved in CH2Cl2 (5 mL). The solution was then added to a solution of 1-phenyl-3-buten-1-ol (888 mg, 6.0 mmol , 1.0 equiv), 4-dimethylaminopyridine (110 mg, 0.9 mmol, 0.15 equiv), and Et3N (1.25 mL, 9.0 mmol, 1.5 equiv) in C2Cl2 (10 mL) under N2 atmosphere at 0° C. (internal). The mixture was allowed to warm to room temperate and was stirred for 2 h. The mixture was then poured to ice water (20 mL) and the aqueous phase was extracted with CH2Cl2 (2×20 mL). The combined organic layers were dried (Na2SO4), filtered and the solvent was removed by rotary evaporation. The residue was purified by chromatography (silica gel, hexane) followed Kugelrohr distillation under reduced pressure to afford 1.25 g (66%) of D-5 as a colorless liquid. to warm to room temperature was stirred for 2 h whereupon a white solid precipitated After removal of solvent and excess dichlorodimethylsilane under reduced pressure, hexane (50 mL) was added the solids were removed by Schlenk filtration After removal of the solvent the residue was dissolved in CH2Cl2 (5 mL) to warm to room temperate was stirred for 2 h the aqueous phase was extracted with CH2Cl2 (2×20 mL) The combined organic layers were dried (Na2SO4) filtered the solvent was removed by rotary evaporation The residue was purified by chromatography (silica gel, hexane) Kugelrohr distillation under reduced pressure to afford 1.25 g (66%) of D-5 as a colorless liquid

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

Procedure: In a 50-mL flask was placed 1-phenyl-3-buten-1-ol (3.19 g, 21.5 mmol) and Et3N (4.48 mL, 32.25 mmol, 1.5 equiv) in CH2Cl2 (30 mL) under N2 atmosphere at 0° C. (ice bath temperature). To the mixture was added dropwise with chlorodimethylvinylsilane (3.86 mL, 28.0 mmol, 1.2 equiv). The mixture was allowed to warm to room temperature and was stirred for 2 h. The mixture was then poured to ice water (30 mL) and was extracted with CH2Cl2 (2×30 mL). The combined organic layers were dried (Na2SO4), filtered and the solvent was removed by rotary evaporation. The residue was distilled under reduced pressure to afford 4.59 g (92%) of 73 as a colorless liquid. In a 50-mL flask was placed at 0° C. was extracted with CH2Cl2 (2×30 mL) The combined organic layers were dried (Na2SO4) filtered the solvent was removed by rotary evaporation The residue was distilled under reduced pressure

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 0.90 ml (3.0 mmol) of tetraisopropoxytitanium and 5 ml of n-butyl ether solution containing allyl bromide (3.0 mmol) was added dropwise at −78° C. 6.2 ml of 0.97M n-butyl ether solution containing isopropylmagnesium bromide (6.0 mmol). After stirring at −50° C. to −40° C. for 1 hour, the reaction liquid was given 0.21 ml (2.1 mmol) of benzaldehyde and heated to 0° C. over 30 minutes. With 10 ml of 3N hydrochloric acid added, the solution was heated to room temperature and separated into layers. The organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate. After drying with anhydrous magnesium sulfate, the solution was freed of solvent by vacuum distillation. The residues were purified by silica gel chromatography. Thus there was obtained 252 mg of 1-phenyl-3-buten-1-ol (81% yields based on benzaldehyde). was added dropwise at −78° C the reaction liquid the solution was heated to room temperature separated into layers The organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate After drying with anhydrous magnesium sulfate the solution was freed of solvent by vacuum distillation The residues were purified by silica gel chromatography

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 0.90 ml (3.0 mmol) of tetraisopropoxytitanium and 5 ml of n-butyl ether solution containing allyl bromide (3.0 mmol) was added dropwise at −78° C. 6.2 ml of 0.97M n-butyl ether solution containing isopropylmagnesium bromide (6.0 mmol). After stirring at −50° C. to −40° C. for 1 hour, the reaction liquid was given 0.21 ml (2.1 mmol) of benzaldehyde and heated to 0° C. over 30 minutes. With 10 ml of 3N hydrochloric acid added, the solution was heated to room temperature and separated into layers. The organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate. After drying with anhydrous magnesium sulfate, the solution was freed of solvent by vacuum distillation. The residues were purified by silica gel chromatography. Thus there was obtained 252 mg of 1-phenyl-3-buten-1-ol (81% yields based on benzaldehyde). was added dropwise at −78° C the reaction liquid the solution was heated to room temperature separated into layers The organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate After drying with anhydrous magnesium sulfate the solution was freed of solvent by vacuum distillation The residues were purified by silica gel chromatography

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

Procedure: To 0.30 ml (1.0 mmol) of tetraisopropoxytitanium and 5 ml of ethyl ether solution containing allyl bromide (1.0 mmol) was added dropwise at −50° C. 1.67 ml of 1.2M ethyl ether solution containing isopropylmagnesium bromide (2.0 mmol). Upon stirring at −50° C. to −40° C. for 1 hour, the reaction liquid turned from yellow into brown. To the reaction liquid was added 0.071 ml (0.7 mmol) of benzaldehyde at −45° C. to −40° C. The temperature was raised to −10° C. to 0° C. over 30 minutes. With 5 ml of 1N hydrochloric acid added, the solution was heated to room temperature and separated into layers. The organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate. After drying with anhydrous magnesium sulfate, the solution was freed of solvent by vacuum distillation. The residues were purified by silica gel chromatography. Thus there was obtained 97 mg of 1-phenyl-3-buten-1-ol (94% yields based on benzaldehyde). was added dropwise at −50° C the reaction liquid To the reaction liquid The temperature was raised to −10° C. to 0° C. over 30 minutes separated into layers The organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate After drying with anhydrous magnesium sulfate the solution was freed of solvent by vacuum distillation The residues were purified by silica gel chromatography

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

Procedure: DIAD (9.0 mL, 45.9 mmol) was added dropwise over 10 min to a stirred solution of 1-phenyl-3-buten-1-ol (4.0 g, 27.0 mmol), PPh3 (10.6 g, 40.5 mmol) and N-methylphenylsulfonamide (6.0 g, 35.0 mmol) in THF (200 mL) under N2 and the resulting mixture was stirred at RT for 20 h. H2O (200 mL) and Et2O (200 mL) were added and separated. The organics were washed with brine (150 mL) and concentrated under reduced pressure while loading on to MgSO4. The mixture was then purified by column chromatography on silica eluting with 3% Et2O/iso-hexanes to yield the sulfonamide (6.45 g, 79%). 1H NMR (CDCl3, 360 MHz) δ 7.78 (2H, d, J=7.8 Hz), 7.53 (1H, t, J=7.8 Hz), 7.44 (2H, t, J=7.8 Hz), 7.30–7.18 (5H, m), 5.67–5.52 (1H, m), 5.20 (1H, t, J=7.8 Hz), 5.02 (1H, dd, J=17.1, 1.5 Hz), 4.93 (1H, dd, J=10.2, 1.3 Hz), 2.70 (1H, app. quintet, J=7.1 Hz), 2.65 (3H, s), 2.44 (1H, app. quintet, J=7.1 Hz). separated The organics were washed with brine (150 mL) concentrated under reduced pressure while loading on to MgSO4 The mixture was then purified by column chromatography on silica eluting with 3% Et2O/iso-hexanes

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

Procedure: DIAD (9.0 mL, 45.9 mmol) was added dropwise over 10 min to a stirred solution of 1-phenyl-3-buten-1-ol (4.0 g, 27.0 mmol), PPh3 (10.6 g, 40.5 mmol) and N-methylphenylsulfonamide (6.0 g, 35.0 mmol) in THF (200 mL) under N2 and the resulting mixture was stirred at RT for 20 h. H2O (200 mL) and Et2O (200 mL) were added and separated. The organics were washed with brine (150 mL) and concentrated under reduced pressure while loading on to MgSO4. The mixture was then purified by column chromatography on silica eluting with 3% Et2O/iso-hexanes to yield the sulfonamide (6.45 g, 79%). 1H NMR (CDCl3, 360 MHz) δ 7.78 (2H, d, J=7.8 Hz), 7.53 (1H, t, J=7.8 Hz), 7.44 (2H, t, J=7.8 Hz), 7.30–7.18 (5H, m), 5.67–5.52 (1H, m), 5.20 (1H, t, J=7.8 Hz), 5.02 (1H, dd, J=17.1, 1.5 Hz), 4.93 (1H, dd, J=10.2, 1.3 Hz), 2.70 (1H, app. quintet, J=7.1 Hz), 2.65 (3H, s), 2.44 (1H, app. quintet, J=7.1 Hz). separated The organics were washed with brine (150 mL) concentrated under reduced pressure while loading on to MgSO4 The mixture was then purified by column chromatography on silica eluting with 3% Et2O/iso-hexanes

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The following procedure for the preparation of allylpinacolboronate ester is representative. A 25-mL round-bottom flask equipped with a magnetic stir bar was charged with magnesium turnings (0.04 g, 1.65 mmol) and fitted with a rubber septum. The flask was purged with argon and charged with dry THF (2.3 mL) followed by PinBH (0.199 mL, 1.37 mmol). To the reaction mixture allylbromide (0.116 mL, 1.37 mmol) was added drop wise with constant stirring over five minutes at 25° C. After stirring for 30 min at 25° C., a second equivalent of allylbromide (0.116 mL, 1.37 mmol) was added. After 90 min of stirring at 25° C. the magnesium turnings were fully consumed and 11B NMR analysis confirmed the complete formation of allylpinacolboronate. Benzaldehyde (0.138 mL, 1.37 mmol) was then added and the reaction mixture was stirred for addition 12 h at 25° C. The reaction mixture was then diluted with hexane (5 mL), quenched with aqueous 1 M HCl (5 mL) and transferred to a separatory funnel. The organic layer was washed with aqueous 1 M NaOH (2×5 mL) and DI water (2×3 mL). The combined organic layers were dried over anhydrous MgSO4, filtered, and dried under vacuo (25° C., 1 Torr) to afford 1-phenyl-3-buten-1-ol as a clear colorless oil; 94.5% (0.190 g). The results for the other allylpinacolborane esters prepared by this method are summarized in Table 3. A 25-mL round-bottom flask equipped with a magnetic stir bar fitted with a rubber septum The flask was purged with argon charged with dry THF (2.3 mL) After stirring for 30 min at 25° C. were fully consumed the reaction mixture was stirred for addition 12 h at 25° C quenched with aqueous 1 M HCl (5 mL) transferred to a separatory funnel The organic layer was washed with aqueous 1 M NaOH (2×5 mL) and DI water (2×3 mL) The combined organic layers were dried over anhydrous MgSO4 filtered dried under vacuo (25° C., 1 Torr)

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

Procedure: Water (0.25 ml) was added to this silica gel supporting scandium (75 mg), and while stirring, 4-phenyl-2-butanone (0.25 mmol) and tetraallyltin (0.125 mmol) were continuously added. The mixture was stirred at 40° C. for 24 hours. The mixture was returned to room temperature, and then was extracted four times by a decantation method using hexane. The solvent was distilled off under reduced pressure, and then the residue was purified by silica gel thin layer chromatography, to obtain the target product, 1-phenyl-3-buten-1-ol. Yield 98%. The mixture was stirred at 40° C. for 24 hours was returned to room temperature was extracted four times by a decantation method The solvent was distilled off under reduced pressure the residue was purified by silica gel thin layer chromatography

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

Procedure: Water (0.25 ml) was added to this silica gel supporting scandium (75 mg), and while stirring, 4-phenyl-2-butanone (0.25 mmol) and tetraallyltin (0.125 mmol) were continuously added. The mixture was stirred at 40° C. for 24 hours. The mixture was returned to room temperature, and then was extracted four times by a decantation method using hexane. The solvent was distilled off under reduced pressure, and then the residue was purified by silica gel thin layer chromatography, to obtain the target product, 1-phenyl-3-buten-1-ol. Yield 98%. The mixture was stirred at 40° C. for 24 hours was returned to room temperature was extracted four times by a decantation method The solvent was distilled off under reduced pressure the residue was purified by silica gel thin layer chromatography

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