The silylalkyne-Prins cyclization: stereoselective synthesis of tetra- and pentasubstituted halodihydropyrans

Org Lett. 2006 Apr 13;8(8):1633-6. doi: 10.1021/ol060247m.

Abstract

[reaction: see text] A new type of Prins cyclization using silylated secondary homopropargylic alcohols and aldehydes yielding tetra- and pentasubstituted dihydropyrans is described. The presence of the trimethylsilyl group in the triple bond favors the Prins cyclization and minimizes the 2-oxonia-[3,3]-sigmatropic rearrangement as a competitive alternative pathway. Ab initio theoretical calculations of the species involved in the rearrangements support the proposed mechanism. The process is highly stereoselective, affording cis-dihydropyran as the only isomer.