4-trimethylsilylcyclohexan-1-one

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

Procedure: To a solution of L-selectride (165 mL, 0.165 mol, 1.5 eq) in anhydrous THF (200 mL) at −78° C. was added dropwise a solution of 4-(trimethylsilyl)cyclohexanone (20 g, 0.11 mol, 1.0 eq) in anhydrous THF (100 mL). The temperature was maintained for 3 h, and then the reaction mixture was stirred at room temperature for 16 h. Then the mixture was cooled to 0° C. before being quenched with water. The resulting mixture was warmed up to room temperature, and then sodium hydroxide aqueous solution (80 mL, 3 M) was added, followed by hydrogen peroxide (80 mL, 30%). After being stirred for 3 h, the mixture was extracted with EtOAc (300 mL×3), and the combined organic layers were washed with H2O and brine, dried over Na2SO4, concentrated to give a residue which was purified by column chromatography on silica gel (petroleum ether/EtOAc=10:1) to obtain the product cis-4-(trimethylsilyl)cyclohexanol as a white solid (10.0 g, 51% yield). The temperature was maintained for 3 h Then the mixture was cooled to 0° C. before being quenched with water The resulting mixture was warmed up to room temperature sodium hydroxide aqueous solution (80 mL, 3 M) was added After being stirred for 3 h the mixture was extracted with EtOAc (300 mL×3) the combined organic layers were washed with H2O and brine dried over Na2SO4 concentrated to give a residue which was purified by column chromatography on silica gel (petroleum ether/EtOAc=10:1)

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

Procedure: Ammonia (100 mL) was condensed at −78° C. (4-methoxyphenyl)trimethylsilane (18.0 g, 0.1 mol, 1.0 eq) in anhydrous Et2O (110 mL) was added followed by EtOH (80 mL) and sodium (23.0 g, 1.0 mol, 10.0 eq) portionwise at −33° C. Additional EtOH (50 mL) was added and ammonia was allowed to evaporated over 16 h. Then water (250 mL) was added to the residue and the mixture was extracted with Et2O (250 mL×3). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The crude product was dissolved in EtOH (20 mL) and H2O (20 mL) and oxalic acid (2.71 g, 0.03 mol, 0.3 eq) was then added. The resulting colorless solution was stirred at room temperature for 2 h. Water (100 mL) was then added and the mixture was extracted with Et2O (100 mL×3). The combined organic extracts were washed with brine, dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The residue was purified by column chromatography on silica gel (petroleum ether/EtOAc=10:1) to furnish 4-(trimethylsilyl)cyclohexanone as a light yellow oil (14.0 g, 72% yield). 1H NMR (300 MHz, CDCl3) δ: 2.44-2.39 (m, 2H), 2.33-2.22 (m, 2H), 2.11-2.05 (m, 2H), 1.53-1.47 (m, 2H), 0.96-0.87 (m, 1H), 0.00 (s, 9H). was added to evaporated over 16 h Then water (250 mL) was added to the residue the mixture was extracted with Et2O (250 mL×3) The combined organic extracts were dried over anhydrous Na2SO4 filtered concentrated in vacuo The crude product was dissolved in EtOH (20 mL) the mixture was extracted with Et2O (100 mL×3) The combined organic extracts were washed with brine dried over anhydrous Na2SO4 filtered concentrated in vacuo The residue was purified by column chromatography on silica gel (petroleum ether/EtOAc=10:1)

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

Procedure: Ammonia (100 mL) was condensed at −78° C. (4-methoxyphenyl)trimethylsilane (18.0 g, 0.1 mol, 1.0 eq) in anhydrous Et2O (110 mL) was added followed by EtOH (80 mL) and sodium (23.0 g, 1.0 mol, 10.0 eq) portionwise at −33° C. Additional EtOH (50 mL) was added and ammonia was allowed to evaporated over 16 h. Then water (250 mL) was added to the residue and the mixture was extracted with Et2O (250 mL×3). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The crude product was dissolved in EtOH (20 mL) and H2O (20 mL) and oxalic acid (2.71 g, 0.03 mol, 0.3 eq) was then added. The resulting colorless solution was stirred at room temperature for 2 h. Water (100 mL) was then added and the mixture was extracted with Et2O (100 mL×3). The combined organic extracts were washed with brine, dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The residue was purified by column chromatography on silica gel (petroleum ether/EtOAc=10:1) to furnish 4-(trimethylsilyl)cyclohexanone as a light yellow oil (14.0 g, 72% yield). 1H NMR (300 MHz, CDCl3) δ: 2.44-2.39 (m, 2H), 2.33-2.22 (m, 2H), 2.11-2.05 (m, 2H), 1.53-1.47 (m, 2H), 0.96-0.87 (m, 1H), 0.00 (s, 9H). was added to evaporated over 16 h Then water (250 mL) was added to the residue the mixture was extracted with Et2O (250 mL×3) The combined organic extracts were dried over anhydrous Na2SO4 filtered concentrated in vacuo The crude product was dissolved in EtOH (20 mL) the mixture was extracted with Et2O (100 mL×3) The combined organic extracts were washed with brine dried over anhydrous Na2SO4 filtered concentrated in vacuo The residue was purified by column chromatography on silica gel (petroleum ether/EtOAc=10:1)

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

Procedure: To a solution of L-selectride (165 mL, 0.165 mol, 1.5 eq) in anhydrous THF (200 mL) at −78° C. was added dropwise a solution of 4-(trimethylsilyl)cyclohexanone (20 g, 0.11 mol, 1.0 eq) in anhydrous THF (100 mL). The temperature was maintained for 3 h, and then the reaction mixture was stirred at room temperature for 16 h. Then the mixture was cooled to 0° C. before being quenched with water. The resulting mixture was warmed up to room temperature, and then sodium hydroxide aqueous solution (80 mL, 3 M) was added, followed by hydrogen peroxide (80 mL, 30%). After being stirred for 3 h, the mixture was extracted with EtOAc (300 mL×3), and the combined organic layers were washed with H2O and brine, dried over Na2SO4, concentrated to give a residue which was purified by column chromatography on silica gel (petroleum ether/EtOAc=10:1) to obtain the product cis-4-(trimethylsilyl)cyclohexanol as a white solid (10.0 g, 51% yield). The temperature was maintained for 3 h Then the mixture was cooled to 0° C. before being quenched with water The resulting mixture was warmed up to room temperature sodium hydroxide aqueous solution (80 mL, 3 M) was added After being stirred for 3 h the mixture was extracted with EtOAc (300 mL×3) the combined organic layers were washed with H2O and brine dried over Na2SO4 concentrated to give a residue which was purified by column chromatography on silica gel (petroleum ether/EtOAc=10:1)

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

Procedure: Ammonia (100 mL) was condensed at −78° C. (4-methoxyphenyl)trimethylsilane (18.0 g, 0.1 mol, 1.0 eq) in anhydrous Et2O (110 mL) was added followed by EtOH (80 mL) and sodium (23.0 g, 1.0 mol, 10.0 eq) portionwise at −33° C. Additional EtOH (50 mL) was added and ammonia was allowed to evaporated over 16 h. Then water (250 mL) was added to the residue and the mixture was extracted with Et2O (250 mL×3). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The crude product was dissolved in EtOH (20 mL) and H2O (20 mL) and oxalic acid (2.71 g, 0.03 mol, 0.3 eq) was then added. The resulting colorless solution was stirred at room temperature for 2 h. Water (100 mL) was then added and the mixture was extracted with Et2O (100 mL×3). The combined organic extracts were washed with brine, dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The residue was purified by column chromatography on silica gel (petroleum ether/EtOAc=10:1) to furnish 4-(trimethylsilyl)cyclohexanone as a light yellow oil (14.0 g, 72% yield). 1H NMR (300 MHz, CDCl3) δ: 2.44-2.39 (m, 2H), 2.33-2.22 (m, 2H), 2.11-2.05 (m, 2H), 1.53-1.47 (m, 2H), 0.96-0.87 (m, 1H), 0.00 (s, 9H). was added to evaporated over 16 h Then water (250 mL) was added to the residue the mixture was extracted with Et2O (250 mL×3) The combined organic extracts were dried over anhydrous Na2SO4 filtered concentrated in vacuo The crude product was dissolved in EtOH (20 mL) the mixture was extracted with Et2O (100 mL×3) The combined organic extracts were washed with brine dried over anhydrous Na2SO4 filtered concentrated in vacuo The residue was purified by column chromatography on silica gel (petroleum ether/EtOAc=10:1)