Rh‐Catalyzed P(III)‐Directed ortho C‐H Borylation of Arylphosphines

Transition‐metal‐mediated metallation 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. Here, we overcome a long‐standing problem on ortho C‐H activation of arylphosphines in a catalytic fashion. Rhodium‐catalyzed ortho‐selective C‐H borylation of various commercially available of arylphosphines with B2pin2 through P(III)‐chelation‐assisted C‐H activation have been developed. This discovery is suggestive of a generic platform that could enable the late‐stage modification of the ready accessible arylphosphines.

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