Abstract

AbstractTransition‐metal‐mediated metalation of an aromatic C−H bond that is adjacent to a tertiary phosphine group in arylphosphines via a four‐membered chelate ring was first discovered in 1968. Herein, we overcome a long‐standing problem with the ortho‐C−H activation of arylphosphines in a catalytic fashion. In particular, we developed a rhodium‐catalyzed ortho‐selective C−H borylation of various commercially available arylphosphines with B2pin2 through PIII‐chelation‐assisted C−H activation. This discovery is suggestive of a generic platform that could enable the late‐stage modification of readily accessible arylphosphines.

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