Cobalt- or Rhodium-Catalyzed Synthesis of 1,2-Dihydrophosphete Oxides via C–H Activation and Formal Phosphoryl Migration

A highly stereo- and chemoselective intermolecular coupling of diverse heterocycles with dialkynylphosphine oxides has been realized via cobalt/rhodium-catalyzed C−H bond activation. This protocol provides an efficient synthetic entry to functionalized 1,2-dihydrophosphete oxides in excellent yields via merger of C-H bond activation and formal 1,2-migration of the phosphoryl group. Compared with traditional methods of synthesis of 1,2-dihydrophosphetes that predominantly relied on stoichiometric metal reagents, this catalytic system features high efficiency, a relatively short reaction time, atomeconomy, and operational simplicity. Photophysical properties of selected 1,2-dihydrophosphete oxides are also disclosed.

(Chem. Sci., 2024, DOI: 10.1039/D4SC00649F.)

Congratulations to Shengbo Xu. Special thanks also go to our collaborators.