Iridium-catalyzed highly enantioselective and chemodivergent coupling reaction of vinyl azides and vinyl benzoxazinones†

Abstract

The first iridium-catalyzed enantioselective coupling reaction of vinyl azides and vinyl benzoxazinones is presented. Vinyl azides underwent a tandem allylic alkylation/interrupted Schmidt rearrangement process to produce enantioenriched 3,4-dihydroquinolin-2(1H)-imines, a new class of N-heterocycles. In the presence of CH₃CO₂H, a conventional asymmetric allylic substitution occurred to provide access to nonracemic allylic amides. The synthetic transformations of the product were carried out to construct chiral amines, amides and N-hetero polycycles.