Transition-Metal Controlled Diastereodivergent Radical Cyclization/Azidation Cascade of 1,7-Enynes

A strategy for achieving diastereodivergent azidations of enynes has been developed, employing azide transfer from the M–N3 complex to alkyl radicals. Following this concept, the diastereoselectivity has been switched by modulating the transition metals and the ligands. The Mn­(III)-mediated radical cyclization/azidation cascade of 1,7-enynes afforded trans-fused pyrrolo­[3,4-c]­quinolinones, whereas the Cu­(II)/bipyridine system gave cis-products.