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The Mechanism and an Improved Asymmetric Allylboration of Ketones Catalyzed by Chiral Biphenols†

Authors

  • David S. Barnett,

    1. Department of Chemistry, Center for Chemical Methodology and Library Development at Boston University (CMLD-BU), Life Science and Engineering Building, Boston University, 24 Cummington Street, Boston, Massachusetts, 02215 (USA), Fax: (+1) 617-353-6466
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  • Philip N. Moquist,

    1. Department of Chemistry, Center for Chemical Methodology and Library Development at Boston University (CMLD-BU), Life Science and Engineering Building, Boston University, 24 Cummington Street, Boston, Massachusetts, 02215 (USA), Fax: (+1) 617-353-6466
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  • Scott E. Schaus Prof. Dr.

    1. Department of Chemistry, Center for Chemical Methodology and Library Development at Boston University (CMLD-BU), Life Science and Engineering Building, Boston University, 24 Cummington Street, Boston, Massachusetts, 02215 (USA), Fax: (+1) 617-353-6466
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  • †

    This research was supported by the NIH (R01 GM078240).

Abstract

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Giving it a boost: A mechanistic study of the enantioselective asymmetric titled reaction with allyldiisopropoxyborane catalyzed by chiral biphenols revealed a key ligand exchange process which liberates isopropyl alcohol. The addition of iPrOH to the reaction increases the overall rate and enantioselectivity. As a result an improved reaction, employing allyldioxaborinane with 1 and tBuOH, resulted in high product yields and enantioselectivities.

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Article Information

DOI

10.1002/anie.200904715

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Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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Keywords

  • boron;
  • homogeneous catalysis;
  • reaction mechanisms;
  • synthetic methods

Publication History

  • Issue online:
  • Version of record online:
  • Manuscript Received:

Funded by

  • NIH. Grant Number: R01 GM078240

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