Three‐Component α‐Thienylation/Oxylation Cascade of I III /S VI‐Ylides via Photoinduced EDA Complex Activation

Herein, a visible‐light‐induced three‐component cascade of a‐thienylation/oxylation of IIII/SVI‐ylides, substituted thiophenes and alcohols is reported. The core of the strategy involves electron‐donor‐acceptor (EDA) complex formation between IIII/SVI‐ylides and electron‐rich thiophenes. Upon photo‐activation, IIII/SVI‐ylides in‐situ generates sulfoxonium ylide radical, which is trapped by thiophenes to generate α‐thienyl‐α'‐ketyl sulfoxonium ylides and initiated subsequent carbenic O‐H insertion from alcohol component. All reactions are operationally simple and proceed smoothly under mild reaction conditions, affording a broad range of unsymmetrical a,a‐disubstituted ketones in moderate to good yields.