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A nickel/N‐heterocyclic carbene catalytic system has been established for decarbonylative borylation of amides with B2nep2 by C−N bond activation. This transformation shows good functional‐group compatibility and can serve as a powerful synthetic tool for late‐stage borylation of amide groups in complex compounds. More importantly, as a key intermediate, the structure of an acyl nickel complex was...
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