2026-09-20T10:41:21Zhttps://dspace.mit.edu/server/oai/request

oai:dspace.mit.edu:1721.1/979882026-06-16T18:16:25Zcom_1721.1_7582com_1721.1_7581col_1721.1_131022

Stephen L. Buchwald. Zhu, Rong, Ph. D. Massachusetts Institute of Technology Massachusetts Institute of Technology. Department of Chemistry. Massachusetts Institute of Technology. Department of Chemistry 2015-07-31T19:12:00Z 2015-07-31T19:12:00Z 2015 2015 http://hdl.handle.net/1721.1/97988 914234194 Thesis: Ph. D. in Organic Chemistry, Massachusetts Institute of Technology, Department of Chemistry, 2015. Cataloged from PDF version of thesis. Vita. Includes bibliographical references. 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. by Rong Zhu. Ph.D. in Organic Chemistry 233 pages eng Massachusetts Institute of Technology 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. http://dspace.mit.edu/handle/1721.1/7582 Chemistry. Development of copper-catalyzed enantioselective alkene difunctionalization reactions via radical intermediates Thesis application/pdf false Publication unknown unknown <Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="002f9d90-4fed-45c5-9140-19fcabc1b44a"> <Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type> <Language>eng</Language> <Title>Development of copper-catalyzed enantioselective alkene difunctionalization reactions via radical intermediates</Title> <PublishedIn> <Publication> </Publication> </PublishedIn> <PublicationDate>2015</PublicationDate> <Authors> <Author> <DisplayName>Zhu, Rong, Ph. D. Massachusetts Institute of Technology</DisplayName> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> </Authors> <Editors> </Editors> <Publishers> <Publisher> <DisplayName>Massachusetts Institute of Technology</DisplayName> <OrgUnit /> </Publisher> </Publishers> <License>http://dspace.mit.edu/handle/1721.1/7582</License> <Keyword>Chemistry.</Keyword> <Abstract>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.</Abstract> <Access xmlns="http://purl.org/coar/access_right" > </Access> </Publication>