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Highly Active Cp*Ir Catalyst at Low Temperatures Bearing an N-Heterocyclic Carbene Ligand and a Chelated Primary Benzylamine in Transfer Hydrogenation

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    Highly Active Cp*Ir Catalyst at Low Temperatures Bearing an N-Heterocyclic Carbene Ligand and a Chelated Primary Benzylamine in Transfer Hydrogenation
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    † Departamento de Quı́mica Inorgánica y Orgánica, Universitat Jaume I, Avda. Sos Baynat s/n, 12071, Castellón, Spain
    ‡ Instituto de Sı́ntesis Quı́mica y Catálisis Homogénea (ISQCH), Departamento de Quı́mica Inorgánica, CSIC-Universidad de Zaragoza, C/Pedro Cerbuna 12, E-50009 Zaragoza, Spain
    *M.B.: e-mail, [email protected]; fax, (+34) 976761187; tel, (+34) 976761184.
    *J.A.M.: e-mail, [email protected]; tel, (+34) 964387516; fax, (+34) 964387522.
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    Organometallics

    Cite this: Organometallics 2014, 33, 23, 6830–6839
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    https://doi.org/10.1021/om500888d
    Published November 21, 2014
    Copyright © 2014 American Chemical Society
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    Abstract

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    The synthesis of new Cp*Ir complexes bearing an N-heterocyclic carbene ligand and a chelated primary benzylamine is described. The new complexes are chiral at metal and have a stereogenic carbon at the benzylamine ligand. The synthesis is diastereoselective, and the origin is thermodynamically controlled. The chiral complexes have been fully characterized. The catalytic results show that the complexes are very active in transfer hydrogenation: for example, acetophenone is reduced to 1-phenylethanol in 2 h at 50 °C using a catalyst loading of 1 mol %. More interestingly is that no base, apart from the required for catalyst activation, is needed in the process. The enantioselectivities obtained range from low to moderate, with a maximum of 58% ee in the case of 2′-methylacetophenone. Initial mechanistic studies by means of DFT calculations suggest that the mechanism is based on a direct hydrogen transfer via a highly ordered transition state centered at the iridium amido group. The calculations are in good agreement with the experimental data and support a concerted one-step mechanism process.

    Copyright © 2014 American Chemical Society

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    Text, tables, figures, CIF files giving details of the catalytic experiments, high-resolution mass spectra (HR/MS), nuclear magnetic resonance (NMR), circular dichroism, X-ray diffraction data, complete ref 25, and computed Cartesian coordinates of all of the molecules reported in this study. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cited By

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    This article is cited by 35 publications.

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    Organometallics

    Cite this: Organometallics 2014, 33, 23, 6830–6839
    Click to copy citationCitation copied!
    https://doi.org/10.1021/om500888d
    Published November 21, 2014
    Copyright © 2014 American Chemical Society
    Request reuse permissions

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