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.

A heterogeneous Pd-Cu NWs-catalyzed expeditious and solvent-free synthesis of propargylamines via A 3 -coupling of aldehydes, alkynes, and amines has been proposed. A wide range of aldehydes, alkynes and amine substrates undergo A 3 -coupling to produce propargylamines in good to excellent yields with good functional tolerance, such as that towards alkoxy, hydroxy, C-X (X = F, Cl, Br) as well as amide and C=C bonds. Furthermore, the catalyst could be recovered easily and reused for at least 5 cycles without showing significant loss of catalytic activity.