Stereoselective Radical Cyclization Cascades Triggered by Addition of Diverse Radicals to Alkynes To Construct 6(5)-6-5 Fused Rings

Cascade-radical cyclization of alkynyl ketones with various carbon-and heteroatom-centered radical precursors via a sequential radical addition/1,5-H radical shift/5-exo-trig/radical cyclization process was realized for the first time. This method provides a strategically novel and step-economical protocol for diversity-oriented synthesis of a wide range of carbocyclic and heterocyclic 6(5)-6-5 fused ring systems with three contiguous stereocenters, including a quaternary carbon in high yields with excellent chemo- and diasteroselectivity.