Selective mono-N-methylation of nitroarenes with methanol catalyzed by atomically dispersed NHC-Ir solid assemblies

• Published in: Journal of catalysis Vol. 389; pp. 337 - 344
• Main Authors: Wang, Jiaquan, Wu, Jiajie, Chen, Zhe-Ning, Wen, Daheng, Chen, Jiangbo, Zheng, Qingshu, Xu, Xin, Tu, Tao
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 01-09-2020
• Subjects: Coordination assemblies; Methanol; mono-N-methylation; NHC-Ir complex; Self-supported catalyst; Self-supported catalyst; NHC-Ir complex; mono-N-methylation; Coordination assemblies; Methanol
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2020.06.004

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•Highly efficient and recyclable catalysts with atomically dispersed catalytic sites.•Selective and effective mono-N-methylation of nitroarenes via one pot tandem reaction.•Using methanol as green carbon source and water is the only byproduct.•Avoiding the usage of toxic reagents.
A series of N-heterocyclic carbene-iridium (NHC-Ir) coordination assemblies based on bis-pyrenoimidazolium salts are prepared, and shown to function as efficient solid molecular catalysts in selective mono-N-methylation of nitroarenes with methanol under mild conditions. The atomically dispersed active Ir(I) centers and the large π-conjugation rings endow the solid catalysts with an exceptionally high activity and selectivity for a broad substrate scope. Such solid NHC-Ir coordination assemblies are robust, which can be easily recovered and reused more than 10 runs without significant loss of their catalytic activity and selectivity. When combined with a subsequent formylation using the same solid catalysts under ambient conditions, this novel protocol can afford diverse formamides in excellent yields, further highlighting the applicability of the present solid catalysts for an efficient diversification of nitroarenes to a broad number of functional amines.