Oxidative Cleavage of Alkoxyamines for Nucleophilic Substitution Reactions

Photoredox catalysis and synthetic electrochemistry have begun to find their spot in a synthetic chemist’s toolbox. Apart from its use of renewable reagents (light and electricity respectively), these methods have enabled pathways that were previously viewed as near impossible. It is therefore essential to develop methods to further advance the field of photoredox catalysis and synthetic electrochemistry. Alkoxyamines previously used for initiation of polymerization reactions are now viewed as prime building blocks for photoredox and synthetic electrochemists for their facile reactivity to oxidatively cleave C‐O bonds. This review begins with addressing the first method developed for generating carbocations via a mesolytic cleavage pathway, and then highlights the recent approaches to utilizing photoredox and synthetic electrochemistry on oxidative cleavage of alkoxyamines for nucleophilic substitution reactions. To demonstrate its applicability, this review also highlights its utilization in the enantioselective synthesis of (‐)‐calycanthidine and (‐)‐psychotriasine.