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Diastereo- and Enantioselective Iridium-Catalyzed Carbonyl Propargylation from the Alcohol or Aldehyde Oxidation Level: 1,3-Enynes as Allenylmetal Equivalents

Authors

  • Dr. Laina M. Geary,

    1. University of Texas at Austin, Department of Chemistry and Biochemistry, 1 University Station—A5300, Austin, TX 78712-1167 (USA)
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  • Dr. Sang Kook Woo,

    1. University of Texas at Austin, Department of Chemistry and Biochemistry, 1 University Station—A5300, Austin, TX 78712-1167 (USA)
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  • Joyce C. Leung,

    1. University of Texas at Austin, Department of Chemistry and Biochemistry, 1 University Station—A5300, Austin, TX 78712-1167 (USA)
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  • Prof. Michael J. Krische

    Corresponding author
    1. University of Texas at Austin, Department of Chemistry and Biochemistry, 1 University Station—A5300, Austin, TX 78712-1167 (USA)
    • University of Texas at Austin, Department of Chemistry and Biochemistry, 1 University Station—A5300, Austin, TX 78712-1167 (USA)
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  • Acknowledgements is made to the Robert A. Welch Foundation (F-0038), the NSF (CHE-1008551), and the Government of Canada’s Banting Postdoctoral Fellowship Program (L.M.G.) for financial support. We thank Dr. Taichiro Touge of Takasago for the generous donation of segphos ligands.

Abstract

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Axial to axial to point chirality transfer: Exposure of conjugated enynes to alcohols in the presence of an iridium catalyst modified by a segphos ligand results in the generation of aldehyde–allenyliridium pairs and formation of enantiomerically enriched products of carbonyl anti-(α-methyl)propargylation (see scheme). An identical set of products are obtained from aldehydes under related transfer hydrogenation conditions by employing formic acid as a reductant.

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