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Transfer hydrogenation reactions catalyzed by chiral half-sandwich Ruthenium complexes derived from Proline

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Abstract

Chiral ruthenium half-sandwich complexes were prepared using a chelating diamine made from proline with a phenyl, ethyl, or benzyl group, instead of hydrogen on one of the coordinating arms. Three of these complexes were obtained as single diastereoisomers and their configuration identified by X-ray crystallography. The complexes are recyclable catalysts for the reduction of ketones to chiral alcohols in water. A ruthenium hydride species is identified as the active species by NMR spectroscopy and isotopic labelling experiments. Maximum enantio-selectivity was attained when a phenyl group was directly attached to the primary amine on the diamine ligand derived from proline.

Transfer hydrogenation of ketones in water can be carried out using water soluble half-sandwich complexes of ruthenium with chiral ligands derived from proline with better enantioselectivity when phenyl groups are on the proline based chiral ligand.

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Acknowledgements

A.G.S. thanks DST, New Delhi for the award of a research grant and A.K. gratefully acknowledges a senior research fellowship from CSIR. Authors thank DST, New Delhi, for providing funds through the FIST program for purchase of a 400 MHz NMR spectrometer.

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Authors and Affiliations

  1. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, 560 012, India

    ARUN KUMAR PANDIA KUMAR & ASHOKA G SAMUELSON

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  1. ARUN KUMAR PANDIA KUMAR
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  2. ASHOKA G SAMUELSON
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Correspondence to ASHOKA G SAMUELSON.

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Supplementary Information (SI)

Mass spectra of complexes (S2–S6), 1H NMR spectrum of ligands and complexes (S7–S19), 1H NMR spectrum of deuterated and undeuterated 1-phenylethanol (S20–S27) and HPLC chromatogram of chiral alcohols (Figures S28–S42) are given in the Supporting Information, available at www.ias.ac.in/chemsci.

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PANDIA KUMAR, A.K., SAMUELSON, A.G. Transfer hydrogenation reactions catalyzed by chiral half-sandwich Ruthenium complexes derived from Proline. J Chem Sci 128, 1405–1415 (2016). https://doi.org/10.1007/s12039-016-1151-8

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  • DOI: https://doi.org/10.1007/s12039-016-1151-8

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