The regioselective [1,3]-allylic transposition of cyclic silyl ethers has been developed. The ring strain of medium-sized rings was found to be an effective controlling element for the ring contraction of eight-membered siloxadienes to form the corresponding six-membered siloxanes. This [1,3]-allylic transposition proceeded in stereospecific manner to generate differently substituted vinylsilanes in good yields, and (Z)-stereochemistry of the endocyclic disubstituted double bond became the (E)-stereochemistry of the resultant pendent alkene after the ring contraction. Overall, the current methodology relying on a streamlined use of a gold-catalyzed intramolecular allylation of silylalkynes, a ruthenium-catalyzed ring-closing metathesis and a rhenium-catalyzed allylic transposition allows en efficient construction of 1,5-diene functionality containing allylic silyloxy moiety. This sequence was successfully applied to an asymmetric synthesis of (�)-amphidinolide V thus highlighting its synthetic utility.

Ring-contractive allylic transposition of silyl ethers and its application to the synthesis of (-)-amphidinolide V

246th National Meeting (2013)

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