Practical iridium-catalyzed direct α-arylation of N-heteroarenes with (hetero)arylboronic acids by H<sub>2</sub>O-mediated H<sub>2</sub> evolution.

Cao, Liang; Zhao, He; Guan, Rongqing; Jiang, Huanfeng; Dixneuf, Pierre H; Zhang, Min · Nat Commun · 2021

basic_science · Level V

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Abstract

Despite the widespread applications of 2-(hetero)aryl N-heteroarenes in numerous fields of science and technology, universal access to such compounds is hampered due to the lack of a general method for their synthesis. Herein, by a H<sub>2</sub>O-mediated H<sub>2</sub>-evolution cross-coupling strategy, we report an iridium(III)-catalyzed facile method to direct α-arylation of N-heteroarenes with both aryl and heteroaryl boronic acids, proceeding with broad substrate scope and excellent functional compatibility, oxidant and reductant-free conditions, operational simplicity, easy scalability, and no need for prefunctionalization of N-heteroarenes. This method is applicable for structural modification of biomedical molecules, and offers a practical route for direct access to 2-(hetero)aryl N-heteroarenes, a class of potential cyclometalated C^N ligands and N^N bidentate ligands that are difficult to prepare with the existing α-C-H arylation methods, thus filling an important gap in the capabilities of synthetic organic chemistry.