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A Highly Tunable Family of Chiral Bisphospholanes for Rh-Catalyzed Enantioselective Hydrogenation Reactions

  1. Jens Holz Dr.1,
  2. Odalys Zayas Dr.1,
  3. Haijun Jiao Dr.1,
  4. Wolfgang Baumann Dr.1,
  5. Anke Spannenberg Dr.1,
  6. Axel Monsees Dr.2,
  7. Thomas H. Riermeier Dr.2,
  8. Juan Almena Dr.2,
  9. Renat Kadyrov Dr.2,
  10. Armin Börner Prof. Dr.1,3

Article first published online: 4 MAY 2006

DOI: 10.1002/chem.200600033

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 12, Issue 19, pages 5001–5013, June 23, 2006

Additional Information

How to Cite

Holz, J., Zayas, O., Jiao, H., Baumann, W., Spannenberg, A., Monsees, A., Riermeier, T. H., Almena, J., Kadyrov, R. and Börner, A. (2006), A Highly Tunable Family of Chiral Bisphospholanes for Rh-Catalyzed Enantioselective Hydrogenation Reactions. Chem. Eur. J., 12: 5001–5013. doi: 10.1002/chem.200600033

Author Information

  1. 1

    Leibniz-Institut für Katalyse e.V. an der Universität Rostock, A.-Einstein-Str. 29a, 18059 Rostock, Germany, Fax: (+49) 381-1281-5000

  2. 2

    Degussa AG, Degussa Homogeneous Catalysts, Rodenbacher Chaussee 4, Building 097, 63457 Hanau-Wolfgang, Germany, Fax: (+49) 6181-59-2417

  3. 3

    Institut für Chemie der Universität Rostock, A.-Einstein-Str. 3a, 18059 Rostock, Germany

Publication History

  1. Issue published online: 16 JUN 2006
  2. Article first published online: 4 MAY 2006
  3. Manuscript Received: 9 JAN 2006

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Keywords:

  • asymmetric catalysis;
  • density functional calculations;
  • hydrogenation;
  • phosphane ligands;
  • rhodium

Abstract

A set of 16 new and closely related bisphospholane ligands have been prepared by using a highly flexible and convergent approach. Each synthesis can be performed on an industrially relevant scale. The bisphosphines differ in the nature of the bridge connecting both phospholane units. Bridges are formed by three-, four-, five- and six-membered heterocyclic or alicyclic rings. Bisphospholanes and their Rh-precatalysts have been investigated by using results of theoretical calculations (DFT) and analytic measurements (31P and 103Rh NMR spectroscopy, X-ray structure analysis). The studies showed that catalysts based on ligands with maleic anhydride or maleimide bridges give constantly superior enantioselectivities in methanol as the solvent. This may account for optimised steric and electronic effects. However, by changing the solvent catalysts with other backbones can give rise to excellent results. This gives proof that simple correlations between steric and electronic properties and results in the enantioselective hydrogenation frequently claimed in literature are not general.

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