Ruthenium‐Catalyzed Tandem Activation of C≡N and B−H Bonds under Dihydrogen: Synthesis of BN Heterocycles

The incorporation of a nitrile function ortho to the B(sp2)HNiPr2 group to obtain cyano(aryl)boranes and subsequent ruthenium‐catalyzed transformation of these cyano(aryl)boranes under a dihydrogen atmosphere (0.1 MPa) provided direct access to NH‐containing 1H‐2,1‐benzazaboroles as BN analogues of indene under very mild conditions (i.e., room temperature). The BN heterocycle could be functionalized from the corresponding lithium amide either by N‐elementation with various p‐block (C, Si, P, B) electrophiles or by palladium‐catalyzed N‐arylation with aryl bromides thus to provide a new and powerful protocol for B−N bond decoration.

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