Visible-Light-Induced Regioselective Radical-Polar Crossover 1,4-Hydrophosphinylation of 1,3-Enynes: Access to Trisubstituted Allenes Bearing a Phosphine Oxide Group.

The radical 1,4-functionalizations of 1,3-enynes have emerged as a powerful strategy for the synthesis of multisubstituted allenes. However, the phosphorus-centered radical-initiated transformations remain largely elusive. Herein, visible-light photoredox catalytic regioselective radical hydrophosphinylation of 1,3-enynes with diaryl phosphine oxides as phosphinoyl radical precursors has been realized. This protocol features mild conditions, a wide substrate scope, and good functional group tolerance, producing a diverse range of phosphinoyl-substituted allenes in moderate to good yields with high atom economy. Detailed mechanistic experiments revealed a radical-polar crossover process in the reaction.

Transition-Metal-Free Anti-Markovnikov Hydroarylation of Alkenes with Aryl Chlorides through Consecutive Photoinduced Electron Transfer.

The hydroarylation of alkenes has emerged as a powerful strategy for arene functionalization. However, aryl chlorides remain a large challenge in this type of reaction due to the chemical inertness of the C(sp2)-Cl bond and high negative reduction potential. Herein, we report an anti-Markovnikov radical hydroarylation of alkenes with aryl chlorides via visible-light photoredox catalysis. The key reactive aryl radicals can be efficiently achieved from aryl chlorides by consecutive photoinduced electron transfer. This transition-metal-free protocol features mild conditions, a wide substrate scope, and functional group tolerance, producing a diverse range of linear alkylarenes in moderate to good yields. The reaction is proposed to proceed through a radical-polar crossover pathway.