A novel dehydrogenative coupling reaction of N-fluorocarboxamides with polyfluoroarenes forming C­(sp2)–C­(sp3) bonds enabled by copper catalysis has been accomplished. N-Fluorocarboxamides are postulated to undergo copper-mediated dehydrogenative cross-coupling reaction with electron-deficient polyfluoroarenes via a radical pathway. Benzylic C–H bonds and aliphatic C–H bonds in N-fluorocarboxamides could proceed smoothly and demonstrated excellent regioselectivity. The detailed mechanism presented is supported by control experiments and density functional theory calculations.

A new Friedel–Crafts acylation generates diverse high-biological value 3-acylindoles, and forms a new C–C bond under transition-metal-free conditions.

C-Aryl glycosides are of high value as drug candidates. Here a novel and cost-effective nickel catalyzed ortho-CAr-H glycosylation reaction with high regioselectivity and excellent α-selectivity is described. This method shows...

A metal-free brand-new one-pot multinitrogenation of amides for the chemo- and regioselective synthesis of 1,5-disubstituted tetrazoles has been developed. By means of electrophilic amide activation, and further C-C bond cleavage and rearrangement, a diverse set of functionalized 1,5-DST derivatives were selectively constructed under mild conditions. As showcased in the mechanisms, the chemoselectivity is easily switched by the selection of the starting materials in the reaction.

A new method for the efficient synthesis of hexahydro-1H-fluorene and octahydrobenzo[a]azulene derivatives through a ring-expansion strategy is reported. With an appropriate combination of thulium(III) trifluoromethanesulfonate and 13X molecular sieves, a range of unsaturated polycyclic compounds were obtained in good yields. Mechanism studies reveal that the reaction is more likely to undergo Meyer−Schuster rearrangement, ring expansion, and Friedel−Crafts-type pathways, which provide a conceptually different strategy for the ring opening of tertiary cycloalkanols.

Construction of C(sp2)−C(sp3) bonds via regioselective coupling of C(sp2)−H/C(sp3)−H bonds is challenging due to the low reactivity and regioselectivity of C−H bonds. Here, a novel photoinduced Ru/photocatalyst-cocatalyzed regioselective cross-dehydrogenative coupling...

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Herein, we describe the copper-catalyzed arylalkylation of activated alkenes via hydrogen-atom transfer and aryl migration strategy. The reaction was carried out through a radical-mediated continuous migration pathway using N-fluorosulfonamides as the alkyl source. The primary, secondary, and tertiary alkyl radicals formed by intramolecular hydrogen-atom transfer proceeded smoothly. This methodology is an efficient approach for the synthesis of various amide derivatives possessing a quaternary carbon center with good yields and high regioselectivity.