Harnessing Energy‐Transfer in N‐Centered Radical‐Mediated Synthesis of Pyrrolidines

Abstract

Atom transfer radical addition (ATRA), cyclization (ATRC), and polymerization (ATRP) are valuable synthetic methods for the functionalization of olefins. With the advent of photoredox catalysis, visible‐light became a popular tool for the initiation of these reactions. We have developed a protocol that enables easy access to distally functionalized pyrrolidines employing blue‐light mediated atom transfer radical [3+2] cyclization. The reaction is scalable, proceeds at very mild conditions. tolerates various functional groups, and provides the corresponding products in good to excellent yields. If rigid olefins are utilized as the reaction partners, the products can be isolated as single diastereomers. The mechanistic investigations provide strong support for an energy‐transfer mechanism.