Efficient cobalt(III)-catalyzed (hetero)aryl and alkenyl C-H hydroarylations of maleimides and maleate esters have been achieved under remarkably mild reaction conditions. Thus, the versatile cobalt(III) catalyst [Cp*CoI(CO)] showed excellent atom-and step-economy as well as high chemo- and site-selectivity providing expedient access to pharmacologically useful succinimides with wide functional group tolerance.

Rhodium(III)-catalyzed C-H bond functionalization for the synthesis of β-aryl aldehydes and ketones from (hetero)aryl oximes, pyri(mi)dine, as well as pyrazoles and α,β-unsaturated carbonyl compounds has been developed under exceedingly mild reaction conditions. Thus, the versatile rhodium(III) catalysis features high step- and atom-economy, oxidant-free reaction conditions, and broad substrate scope.

An efficient cobalt-catalyzed difluoroalkylation/ Giese radical conjugate cyclization manifold with various alkyne-tethered cyclohexadienones and halogenated fluorinating reagents was accomplished under remarkable mild reaction conditions, thus providing an expedient route to valuable fluorinated chromens. The utility of this transformation was demonstrated by high site selectivity as well as chemo-and diastereoselectivity, broad substrate scope, excellent functional group tolerance, and facile late-stage modification.

An efficient copper(I)-catalyzed oxydifluoroalkylation of unsaturated carboxylic acids has been developed under mild reaction conditions. Various α-bromodifluoromethyl substituted heterocycles, esters, amides, and ketones were successfully employed as the CF source. This cost-effective copper(I) catalysis provides expedient access to high valued lactones with ample substrate scope, wide functional group tolerance, and up to 98% yield.

A set of copper-catalyzed sulfonylcyanations of vinylarenes with readily accessible arylsulfonyl chlorides and trimethyl cyanide was achieved, providing a streamlined route to various decorated β-sulfonyl nitriles with good regioselectivity and functional group tolerance.