Development of copper-catalyzed enantioselective alkene difunctionalization reactions via radical intermediates

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.

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2015

Author dc:creator

• Zhu, Rong, Ph. D. Massachusetts Institute of Technology

Advisor dc:contributor.advisor

• Stephen L. Buchwald.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/97988

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/97988