Diastereoselective Construction of α‐Silyltetrahydropyranols through Silyl‐Oxa‐Prins Cyclization

The Bronsted acid mediated selective silyl-oxa-Prins cyclization of α-silyloxy homoallylsilanes with various aldehydes was achieved. Synthetically valuable α-silyltetrahydropyranol products were obtained in high yields with excellent diastereoselectivities. Both syn- and anti-isomeric tetrahydropyranols were selectively obtained by tuning the olefinic geometry of the substrates. The procedure is operationally simple and convenient to perform even on a large scale under mild conditions.