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Rhenium-catalysed C(sp3)–H bond borylation in the absence of any oxidant, hydrogen acceptor, or external ligand, with the generation of H2 as the sole byproduct is described. The transformation, which represents a rare example of rhenium-catalysed C(sp3)–H bond functionalisation, features high atom efficiency and simple reaction conditions.

Graphical abstract: Rhenium-catalysed dehydrogenative borylation of primary and secondary C(sp3)–H bonds adjacent to a nitrogen atom

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