Radical‐Polar Crossover Annulation: A Platform for Accessing Polycyclic Cyclopropanes.

Photoredox‐mediated radical/polar crossover (RPC) processes provide unique solutions to challenging annulations. Herein, we describe an approach to the cyclopropanation of olefins that are embedded within bicyclic scaffolds. Whereas these systems are notoriously recalcitrant toward classical cyclopropanation approaches, RPC cyclopropanation can be executed with ease, leading to polycarbocyclic and polyheterocyclic cyclopropanes. The cyclopropanation proceeds through a photoredox‐enabled Giese‐type radical addition followed by an intramolecular anionic substitution reaction on a neopentyl leaving group. [ABSTRACT FROM AUTHOR]