Elsevier

Tetrahedron Letters

Volume 54, Issue 21, 22 May 2013, Pages 2674-2678
Tetrahedron Letters

Catalytic hydrogenation of unactivated amides enabled by hydrogenation of catalyst precursor

https://doi.org/10.1016/j.tetlet.2013.03.047Get rights and content

Abstract

A general method for catalytic hydrogenation of unactivated amides was achieved. During the catalyst induction period, a novel structural change was observed involving full hydrogenation of the interior unsaturated bonds of the pyridines of the Ru-containing catalyst precursor. Based on this observation, the mechanism of amide hydrogenation may involve a two-step pathway, wherein the Ru catalyst having an H–Ru–N–H functionality is generated in the first step, followed by the amide carbonyl group interacting with the outer, rather than the inner, sphere of the Ru catalyst.

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Acknowledgments

This work was supported by Grant-in-Aid for Scientific Research on Innovative Areas ‘Molecular Activation Directed toward Straightforward Synthesis’, MEXT. T.M. and S.O. acknowledge IGER in chemistry at Nagoya University (NU) and JSPS for financial support. The authors wish to thank Dr. K. Oyama and Y. Maeda (Chemical Instrument Facility of RCMS) for NMR and ESI-MS measurements and Professor R. Noyori (NU & RIKEN) for fruitful discussions.

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