Get access

Umpolung Reactivity in the Stereoselective Synthesis of S-Linked 2-Deoxyglycosides

Authors

  • Kedar N. Baryal,

    1. Department of Chemistry and School of Green Chemistry and Engineering, The University of Toledo, 2801 W. Bancroft Street, Toledo, OH 43606 (USA)
    Search for more papers by this author
  • Danyang Zhu,

    1. Department of Chemistry and School of Green Chemistry and Engineering, The University of Toledo, 2801 W. Bancroft Street, Toledo, OH 43606 (USA)
    Search for more papers by this author
  • Dr. Xiaohua Li,

    1. Department of Chemistry and School of Green Chemistry and Engineering, The University of Toledo, 2801 W. Bancroft Street, Toledo, OH 43606 (USA)
    Search for more papers by this author
  • Prof. Dr. Jianglong Zhu

    Corresponding author
    1. Department of Chemistry and School of Green Chemistry and Engineering, The University of Toledo, 2801 W. Bancroft Street, Toledo, OH 43606 (USA)
    • Department of Chemistry and School of Green Chemistry and Engineering, The University of Toledo, 2801 W. Bancroft Street, Toledo, OH 43606 (USA)
    Search for more papers by this author

  • Presented in part at the 244th American Chemical Society National Meeting, Philadelphia, PA, USA, August 19–23, 2012, CARB-13. We are very grateful to the National Science Foundation (CHE-1213352) and the University of Toledo for supporting this research. We thank Professors Peter Andreana and Steve Sucheck for proofreading this manuscript and Joseph Duffey, Hanin Dughayli, and Mallory Walker for experimental assistance.

Abstract

original image

Take control! An unprecedented sulfenylation of stereochemically defined 2-deoxyglycosyl lithium species with asymmetric sugar-derived disulfide acceptors enabled the stereoselective synthesis of both α- and β-S-linked 2-deoxyoligosaccharides. Reductive lithiation of 2-deoxyglycosyl phenylsulfides at −78 °C provides predominantly axial glycosyl lithium species, which upon warming isomerize to predominantly equatorial lithium species (see scheme).

Get access to the full text of this article

Ancillary