Cobalt-Catalyzed Enantioselective Radical Hydroamination of Alkenes with N-Fluorobenzenesulfonimides: Theoretical Insight of Enantio-Determining SN2-like Reductive Elimination

Abstract

The cobalt-catalyzed enantioselective radical hydroamination of alkenes with N-fluorobenzenesulfonimides has been systematically investigated using density functional theory (DFT) calculations. The favorable reaction mechanism consists of six key processes: halogen atom transfer (XAT), N-centered radical addition, transmetalation, hydrogen atom transfer (HAT), C-centered radical addition, and SN2-like reductive elimination. The HAT process is the step that determines regioselectivity. The SN2-like reductive elimination serves as both the enantio-determining step and the rate-determining step of the catalytic cycle. Additionally, the origins of regioselectivity and enantioselectivity have been analyzed from the perspectives of distortion and interaction. This theoretical study offers valuable insights into the activity and selectivity of cobalt-catalyzed enantioselective radical hydroamination at both molecular and atomic levels, aiding the development of asymmetric synthesis.