An Enamide-Based Domino Reaction for a Highly Stereoselective Synthesis of Tetrahydropyrans

Angew Chem Int Ed Engl. 2019 Sep 9;58(37):13056-13059. doi: 10.1002/anie.201907565. Epub 2019 Aug 7.

Abstract

A novel method for the highly stereoselective synthesis of tetrahydropyrans is reported. This domino reaction is based on a twofold addition of enamides to aldehydes followed by a subsequent cyclization and furnishes fully substituted tetrahydropyrans in high yields. Three new σ-bonds and five continuous stereogenic centers are formed in this one-pot process with a remarkable degree of diastereoselectivity. In most cases, the formation of only one out of 16 possible diastereomers is observed. Two different stereoisomers can be accessed in a controlled fashion starting either from an E- or a Z-configured enamide.

Keywords: Lewis acids; domino reactions; enamides; stereoselective synthesis; tetrahydropyrans.