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Hydrogenation of Polar Bonds Catalysed by Ruthenium-Pincer Complexes

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Ruthenium in Catalysis

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 48))

Abstract

Catalytic hydrogenation of polar bonds using molecular hydrogen is an important, atom-economical synthetic reaction. Classical reduction methods of polar bond often require reactive metal-hydride reagents in stoichiometric amount and produce copious waste. Hydrogenation of carbonyl compounds in particular provides ‘green’ approaches to synthetically important building blocks, such as alcohols and amines. We have designed and synthesized several ruthenium-based pincer catalysts for unprecedented hydrogenation reactions including: (1) amides to alcohols and amines, (2) biomass-derived di-esters to 1,2-diols and (3) CO2 and CO derivatives to methanol. These atom-economical reactions operate under neutral, homogeneous conditions, at mild temperatures, mild hydrogen pressures, and can operate in absence of solvent with no generation of waste. The postulated mechanisms involve metal–ligand cooperation (MLC) by aromatization–dearomatization of the heteroaromatic pincer core.

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Acknowledgements

Supported by the European Research Council (ERC) under the FP7 framework (No. 246837), Kimmel Center for Molecular Design and CSIR-NCL (start-up grant to E.B, MLP028726). D.M. is the Israel Matz Professorial Chair of Organic Chemistry.

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Authors and Affiliations

  1. Catalysis Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pashan, Pune, 411008, India

    Ekambaram Balaraman

  2. Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel

    David Milstein

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  1. Ekambaram Balaraman
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  2. David Milstein
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Correspondence to Ekambaram Balaraman .

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Editors and Affiliations

  1. Inst. des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université Rennes1, Rennes, France

    Pierre H. Dixneuf

  2. Inst. des Sciences Chimiques de Rennes, UMR 6226-CNRS-Université de Rennes1, Rennes, France

    Christian Bruneau

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Balaraman, E., Milstein, D. (2014). Hydrogenation of Polar Bonds Catalysed by Ruthenium-Pincer Complexes. In: Dixneuf, P., Bruneau, C. (eds) Ruthenium in Catalysis. Topics in Organometallic Chemistry, vol 48. Springer, Cham. https://doi.org/10.1007/3418_2014_77

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