Affiliation:
1. Department of Chemistry University of Pittsburgh Pittsburgh Pennsylvania 15260 USA
Abstract
AbstractAcyliminium ions and related species are potent electrophiles that can be quite valuable in the synthesis of nitrogen‐containing molecules. This manuscript describes a protocol to form these intermediates through hydride abstractions of easily accessible allylic carbamates, amides, and sulfonamides that avoids the reversibility that is possible in classical condensation‐based routes. These intermediates are used in the preparation of a range of nitrogen‐containing heterocycles, and in many cases high levels of stereocontrol are observed. Specifically areas of investigation include the impact of chemical structure on oxidation efficiency, the geometry of the intermediate iminium ions, the impact of a substrate stereocenter on stereocontrol, and an examination of transition state geometry.
Funder
Directorate for Mathematical and Physical Sciences
National Coordination Office
Subject
General Chemistry,Catalysis,Organic Chemistry