1,2-Alkynyl Functionalization of Unactivated Alkenes via Diverse Radical-Triggered Functional Group Migration.

We have developed a transition-metal-free radical approach for 1,2-alkynyl functionalization of unactivated alkenes through the combination of 3-exo-dig cyclization with alkynyl migration triggered by in situ-generated diverse radical precursors. This strategy provides a robust toolkit to access a variety of synthetically important α-functionalized alkynyl ketones, simultaneously installing densely functionalized carbonyl, alkynyl, and other various functional groups into the alkenes. The broad substrate scope, which includes distinctly electron-donating or electron-withdrawing alkynyl migrating groups, excellent functional group compatibility, and remarkable selectivity make this protocol practical and attractive.