Reductive cross-coupling has emerged as a direct method for the construction of carbon-carbon bonds. Most cobalt-, nickel-, and palladium-catalyzed reductive cross-coupling reactions to date are limited to stoichiometric Mn(0) or Zn(0) as the reductant. One nickel-catalyzed cross-coupling paradigm using Et3N as the terminal reductant is reported. By using this photoredox catalysis and nickel catalysis approach, a direct Csp(2)-Csp(3) reductive cross-coupling of aryl bromides with alkyl bromides is achieved under mild conditions without stoichiometric metal reductants.

A novel palladium-catalyzed C-H double carbonylation introduces two adjacent carbonyl groups for the synthesis of isatins from readily available anilines. The reaction proceeds under atmospheric pressure of CO with high regioselectivity and without any additives. Density functional theory investigations indicate that the palladium-catalyzed double carbonylation catalytic cycle is plausible.

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β-Lactam scaffolds are considered to be ideal building blocks for the synthesis of nitrogen-containing compounds. A new palladium-catalyzed oxidative carbonylation of N-allylamines for the synthesis of α-methylene-β-lactams is reported. DFT calculations suggest that the formation of β-lactams via a four-membered-ring transition state is favorable.

Transition-metal-catalyzed oxidative C−H/N−H coupling reaction is an important method to construct C−N bonds. However, stoichiometric oxidants were usually necessary. Here, we report a palladium-catalyzed electro-oxidative intramolecular C−H/N-H annulation reaction without an external oxidant or additive. A variety of pyrido[1,2-a]benzimidazoles were constructed by a simple, green, and mild path. Experimental results suggested that Pd(0) could be oxidized on the anode to be recycled.