Nickel catalyzed C-N coupling of haloarenes with B<sub>2</sub>N<sub>4</sub> reagents.

Chang, Qianqian; Li, Qini; Deng, Yi-Hui; Sun, Tian-Yu; Wu, Yun-Dong; Wang, Leifeng · Nat Commun · 2025

basic_science · Level V

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Abstract

Carbon-heteroatom bond (especially for C-N bond) formation through nickel catalysis has seen significant development. Well-established Ni(0)/Ni(II) redox cycle and photoinduced Ni(I)/Ni(III) redox cycle have been the dominant mechanisms. We report a thermally driven Ni-catalyzed method for C-N bond formation between haloarenes and B<sub>2</sub>N<sub>4</sub> reagents, yielding N,N-dialkylaniline derivatives in good to excellent yields with broad functional group tolerance under base-free conditions. The catalytic protocol is useful for base-sensitive structures and late-stage modifications of complex molecules. Detailed mechanistic studies and density functional theory (DFT) calculations indicate that a Ni(I)/Ni(III) redox cycle is preferred in the C-N coupling process, and B<sub>2</sub>N<sub>4</sub> reagent serves both as a single electron transfer donor and a N,N-dialkylation source.