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Highly selective hydrogenation of amides catalysed by a molybdenum pincer complex: scope and mechanism

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Abstract

A series of molybdenum pincer complexes has been shown for the first time to be active in the catalytic hydrogenation of amides. Among the tested catalysts, Mo-1a proved to be particularly well suited for the selective C–N hydrogenolysis of N-methylated formanilides. Notably, high chemoselectivity was observed in the presence of certain reducible groups including even other amides. The general catalytic performance as well as selectivity issues could be rationalized taking an anionic Mo(0) as the active species. The interplay between the amide C[double bond, length as m-dash]O reduction and the catalyst poisoning by primary amides accounts for the selective hydrogenation of N-methylated formanilides. The catalyst resting state was found to be a Mo–alkoxo complex formed by reaction with the alcohol product. This species plays two opposed roles – it facilitates the protolytic cleavage of the C–N bond but it encumbers the activation of hydrogen.

Graphical abstract: Highly selective hydrogenation of amides catalysed by a molybdenum pincer complex: scope and mechanism

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Publication details

The article was received on 12 Jul 2019, accepted on 21 Sep 2019 and first published on 08 Oct 2019


Article type: Edge Article
DOI: 10.1039/C9SC03453F
Chem. Sci., 2019, Advance Article
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    Highly selective hydrogenation of amides catalysed by a molybdenum pincer complex: scope and mechanism

    T. Leischner, L. Artús Suarez, A. Spannenberg, K. Junge, A. Nova and M. Beller, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C9SC03453F

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