Unexpected Domino Silyl-Prins/Aryl Migration Process from Geminal Vinylsilyl Alcohols

[Image: see text] The silyl-Prins cyclization of geminal vinylsilyl alcohols and aldehydes, promoted by TMSOTf, provides access to polysubstituted tetrahydropyrans in which the silyl group remains in the molecule and an aryl group has migrated from silicon to carbon. This domino silyl-Prins/aryl migration process is general and high-yielding for aryl, vinyl, or alkyl aldehydes. Moreover, cyclization proceeds with very high stereocontrol in a one-pot reaction in which both quaternary and tertiary stereogenic centers have been created.