A nickel-catalyzed cross-electrophile coupling reaction between (hetero)­aryl bromides and 2,2-difluorovinyl tosylate is presented. This protocol provides facile incorporation of the gem-difluorovinyl moiety in organic molecules. The method features mild reaction conditions, good functional group tolerance, and excellent yields. Furthermore, mechanistic experiments and DFT studies indicate a Ni(0)/Ni­(II) catalytic cycle, thus differing from the currently accepted catalytic cycle for nickel-catalyzed C­(sp2)–C­(sp2) cross-electrophile coupling reactions.

A cross-electrophile coupling between gem-difluorinated cyclopropanes and 2,2-difluorovinyl tosylate via dual Ni/Pd cooperative catalysis under mild reaction conditions is presented. Various structurally unique organofluorine compounds bearing both monofluoroalkene and gem-difluoroalkene moieties can be effectively afforded in good yields with a high (Z)-selectivity. The synthetic utility of this protocol has been successfully demonstrated by the late-stage modification of a series of complex bioactive molecules.

A ligand-free iron-catalyzed method for the oxygenation of benzylic sp3 C–H bonds by molecular oxygen (1 atm) using a thiyl radical as a cocatalyst has been developed.

A copper-catalyzed four-component trifluoromethylthio-arylsulfonylation between styrene derivatives, AgSCF3, aryldiazonium tetrafluoroborates, and ex situ generated sulfur dioxide (from SOgen) is presented. This reaction features mild reaction conditions, good functional group tolerance, a broad substrate scope, good yields, and excellent diastereoselectivity. Preliminary mechanistic studies revealed that a radical process might be involved in this transformation.