Regio‐ and Stereospecific Cleavage of Silyl‐ and Disilylepoxides with Lithium Diphenylphosphide

Abstract Unsubstituted or α‐ and β‐C‐substituted silylepoxides react stereospecifically with lithium diphenylphosphide, optionally followed by methylation, to give vinylphosphonium iodides or vinylphosphine oxides resulting from α‐opening and silyl enol ethers, vinylsilanes or α‐hydroxysilanes by β‐opening. On the other hand, α,β‐ or α,α‐disilylepoxides afforded β‐silyl vinylphosphine oxides or α‐silylated silyl enol ethers by α‐ and β‐cleavage, respectively. All compounds are interesting synthons in organic chemistry.