Stereoselective Atom Transfer

Summary

Principal Investigator: KARL BARRY SHARPLESS
Abstract: Olefins provide a most efficient entry to organic compounds with diverse and controllable functionality. The goals of this program are to discover and improve a variety of methods for selective olefin oxidation, including osmium-catalyzed aminohydroxylation and dihydroxylation, rhenium-catalyzed epoxidation, bromine-catalyzed aziridination, and ruthenium tetroxide catalyzed oxidation reactions. Emphasis is placed on catalytic aminohydroxylation in both racemic and enantioselective modes, as this problem presents both the greatest challenges and the great potential rewards for synthetic utility. Preliminary results have provided exciting mechanistic insights in this area. Additionally, single-atom transfers mediated by osmium and other d(0)-metals, based on the exploration of the "spectator-oxo" principle, will be studied. This heretofore little explored reactivity should greatly expand the scope of the transition metal-mediated oxidation processes. The products of olefin oxidation of greatest importance as synthetic intermediates are high-energy compounds that engage in rapid and selective subsequent transformations. Chief among these are epoxides, aziridines, cyclic sulfates, and episulfonium ions. New methods for the synthesis and manipulation of these intermediates are discussed. The ultimate goal is the development and exploitation of an expanded set of highly reliable reactions for the preparation of organic compounds of use to the exciting disciplines of diversity chemistry and drug discovery.
Funding Period: ----------------2009 - ---------------2011-
more information: NIH RePORT

Top Publications

  1. ncbi Practical synthesis of amides from in situ generated copper(I) acetylides and sulfonyl azides
    Michael P Cassidy
    Department of Chemistry, Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA
    Angew Chem Int Ed Engl 45:3154-7. 2006
  2. ncbi Copper-catalyzed reaction cascade: direct conversion of alkynes into N-sulfonylazetidin-2-imines
    Matthew Whiting
    Department of Chemistry, Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA
    Angew Chem Int Ed Engl 45:3157-61. 2006
  3. ncbi Efficient synthesis of 2-substituted-1,2,3-triazoles
    Jarosław Kalisiak
    Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA
    Org Lett 10:3171-4. 2008

Detail Information

Publications4

  1. ncbi Practical synthesis of amides from in situ generated copper(I) acetylides and sulfonyl azides
    Michael P Cassidy
    Department of Chemistry, Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA
    Angew Chem Int Ed Engl 45:3154-7. 2006
  2. ncbi Copper-catalyzed reaction cascade: direct conversion of alkynes into N-sulfonylazetidin-2-imines
    Matthew Whiting
    Department of Chemistry, Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA
    Angew Chem Int Ed Engl 45:3157-61. 2006
  3. ncbi Efficient synthesis of 2-substituted-1,2,3-triazoles
    Jarosław Kalisiak
    Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA
    Org Lett 10:3171-4. 2008
    ..The hydroxymethyl group can also be removed, providing convenient access to N H-1,2,3-triazoles. The reaction is experimentally simple and readily scalable...