Acetic Acid → 4-((Tert-butyldimethylsilyl)oxy)-4-methylpent-2-ynal

Participants

Reaction Conditions

Reaction Steps

To a solution of 50.0 g (252 mmol) (1,1-dimethylethyl)[(1,1-dimethyl-2-propynyl)oxy]dimethylsilane in 200 mL of tetrahydrofuran (THF) at -70° C. was added 112 mL (280 mmol) of 2.5M butyl lithium (BuLi) in hexanes dropwise over 25 min., keeping the temperature below -55° C. The mixture was stirred for 5 minutes. Then, 50 mL of dimethylformamide (DMF) was added dropwise over 10 minutes. After 15 minutes, the reaction was quenched by the addition of 32 mL of acetic acid (560 mmol). After the mixture was allowed to warm to -20° C., 200 mL of hexane and 200 mL of water were added. The aqueous layer was back-extracted with 100 mL of hexane. The combined organic layers were washed with 200 mL of saturated aqueous NH4Cl solution and then with 200 mL of brine. After drying over sodium sulfate, the solution was concentrated to dryness. Then the residue was distilled through a 10-cm Vigreaux column to give 48.8 g (85.5% yield) of 4-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-4-methyl-2-pentynal: bp 50° C. (0.5 mm Hg).

Provenance & Evidence