Size‐Exclusion Borane‐Catalyzed Domino 1,3‐Allylic/Reductive Ireland–Claisen Rearrangements: Impact of the Electronic and Structural Parameters on the 1,3‐Allylic Shift Aptitude

Abstract

The reductive Ireland-Claisen rearrangement through borane-mediated hydrosilylation is reported. The method employs a borane catalyst with a special structural design and affords access to synthetically relevant products with high diastereoselectivity. Depending on electronic and structural parameters, the reaction can be coupled with a 1,3-allylic shift, thus the valence isomer of the Ireland-Claisen product is formed.