Cobalt-catalysed sp² C–H bond functionalization has attracted considerable attention in recent years because of the low cost of cobalt complexes and interesting modes of action in the process. In comparison, much less efforts have been devoted to the sp³ carbons. Here we report the cobalt-catalysed site-selective dehydrogenative cyclization of aliphatic amides via a C–H bond functionalization process on unactivated sp³ carbons with the assistance of a bidentate directing group. This method provides a straightforward synthesis of monocyclic and spiro β- or γ-lactams with good to excellent stereoselectivity and functional group tolerance. In addition, a new procedure has been developed to selectively remove the directing group, which enables the synthesis of free β- or γ-lactam compounds. Furthermore, the first cobalt-catalysed intermolecular dehydrogenative amination of unactivated sp³ carbons is also realized.

Over the past years, impressive progress has been made on the development of the chemoselective and direct formation of carbon–carbon and carbon–heteroatom bonds involving internal alkynes under catalytic oxidative systems. These transformations heavily rely on the in situ generation of reactive radical intermediates that are initiated by oxidants, visible light photocatalysis, or electrocatalysis and so on. Numerous chemically and biomedically important building blocks have been synthesized, and will continue to be obtained by taking advantage of the radical transformation of internal alkynes in the following years. In this review, we highlight the recent progress in this rapidly growing area by presenting a series of catalytic oxidative reactions, mechanisms and applications which have appeared in the most recent literature.