Affiliation:
1. Department of Chemistry University of Illinois at Chicago 845 W Taylor St., MC 111 Chicago IL 60607 USA
2. Department of Process Research & Development Merck & Co., Inc. 126 Lincoln Ave Rahway NJ 07065 USA
Abstract
AbstractThe roles of substituent and solvent effects in promoting the 4π electrocyclization of N‐alkenylnitrones to give azetidine nitrones have been investigated by experimental examination of relative rates, activation energies, and linear free energy relationships. These transformations are synthetically important because they favor the formation of a strained heterocyclic ring with imbedded functionality and stereochemical information for versatile derivatization. Mechanistic investigations, including Hammett studies, solvent‐dependent Eyring studies, and solvent isotope effects, provide insight into the steric and electronic factors that control these electrocyclizations and identify trends that can be used to advance this approach towards the rapid synthesis of complex azetidines.
Funder
National Science Foundation
Subject
General Chemistry,Catalysis,Organic Chemistry