Development of copper-catalyzed enantioselective alkene difunctionalization reactions via radical intermediates
Author(s)Zhu, Rong, Ph. D. Massachusetts Institute of Technology
Massachusetts Institute of Technology. Department of Chemistry.
Stephen L. Buchwald.
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Chapter 1 A mild, versatile, and convenient method for the efficient oxytrifluoromethylation of unactivated alkenes based on a copper-catalyzed ligand-assisted difunctionalization strategy has been developed. This method provides access to a variety of classes of synthetically useful CF3-containing building blocks from simple starting materials. Chapter 2 A method for the efficient enantioselective oxytrifluoromethylation of alkenes has been developed using a copper catalyst system inspired by the ligand dependence observed in the racemic reaction. Mechanistic studies are consistent with a metal-catalyzed redox radical addition mechanism, in which a C-0 bond is formed via the copper-mediated enantioselective trapping of a prochiral alkyl radical intermediate derived from the initial trifluoromethyl radical addition. Chapter 3 A general and versatile method for the catalytic enantioselective oxyfunctionalization of alkenes has been developed based on a key Cu-mediated enantioselective C-0 bond forming process of prochiral alkyl radical intermediates. A wide range of radicals were found to participate this type of reaction, including azidyl, arylsulfonyl, aryl, acyloxyl and alkyl radicals. This method provides rapid access to a broad spectrum of interesting enantiomerically enriched lactones through tandem C-N/C-O, C-S/C-O, C-Cary/aIkyI/C-O or C-O/C-O bond formation, in good yields and enantiomeric excesses with good functional group compatibility.
Thesis: Ph. D. in Organic Chemistry, Massachusetts Institute of Technology, Department of Chemistry, 2015.Cataloged from PDF version of thesis. Vita.Includes bibliographical references.
DepartmentMassachusetts Institute of Technology. Department of Chemistry.
Massachusetts Institute of Technology