Abstract

AbstractThe paper describes an asymmetric approach to the synthesis of the (2S,4S,6S)‐2,4,6‐trimethylnonyl segment of siphonarienes. The key step used is a newly developed methodology to obtain sec‐dialkyl acetylenes based on the intramolecular hydride transfer from a secondary γ‐benzyloxy group with well‐defined absolute stereochemistry, ensured by a Sharpless asymmetric epoxidation reaction, to a cation generated by Lewis acid treatment of a tertiary Co2(CO)6‐complexed propargylic alcohol.

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