Practical iridium-catalyzed direct α-arylation of N-heteroarenes with (hetero)arylboronic acids by H2O-mediated H2 evolution

Liang Cao; He Zhao; Rongqing Guan; Huanfeng Jiang; Pierre H Dixneuf; Min Zhang

doi:10.1038/s41467-021-24468-z

Practical iridium-catalyzed direct α-arylation of N-heteroarenes with (hetero)arylboronic acids by H₂O-mediated H₂ evolution

Nat Commun. 2021 Jul 9;12(1):4206. doi: 10.1038/s41467-021-24468-z.

Authors

Liang Cao¹, He Zhao¹, Rongqing Guan¹, Huanfeng Jiang¹, Pierre H Dixneuf², Min Zhang³

Affiliations

¹ Key Lab of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, China.
² University of Rennes, ISCR, Rennes, France.
³ Key Lab of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, China. minzhang@scut.edu.cn.

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 H₂O-mediated H₂-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.

Publication types

Research Support, Non-U.S. Gov't