2026-09-19T21:08:49Zhttps://dspace.mit.edu/server/oai/requestoai:dspace.mit.edu:1721.1/930352026-06-16T18:16:29Zcom_1721.1_7582com_1721.1_7581col_1721.1_131022
Gregory C. Fu.
Lee, Sarah Yunmi
Massachusetts Institute of Technology. Department of Chemistry.
Massachusetts Institute of Technology. Department of Chemistry
2015-01-20T17:56:24Z
2015-01-20T17:56:24Z
2014
2014
http://hdl.handle.net/1721.1/93035
899242342
Thesis: Ph. D. in Organic Chemistry, Massachusetts Institute of Technology, Department of Chemistry, 2014.
Cataloged from PDF version of thesis. Vita.
Includes bibliographical references.
Chapter 1 describes the development and detailed mechanistic investigation of the first non-enzymatic method for the dynamic kinetic resolution of secondary alcohols via enantioselective acylation, with acetyl isopropyl carbonate, through the use of a planar-chiral DMAP derivative (an acylation catalyst) in combination with a ruthenium complex (an alcohol-racemization catalyst). Chapter 2 describes the development and detailed mechanistic investigation of the enantioselective synthesis of tertiary alkyl fluorides via the [alpha]-fluorination of ketenes catalyzed by a planar-chiral nucleophile with N-fluorodibenzenesulfonimide in the presence of sodium pentafluorophenoxide. Chapter 3 describes the development and preliminary mechanistic study of the first asymmetric, phosphine-catalyzed intramolecular [3 + 2] cycloadditions of allenes with alkenes that furnish an array of diastereomerically pure bicyclic compounds bearing two or three contiguous tertiary! quaternary stereocenters.
by Sarah Yunmi Lee.
Ph.D. in Organic Chemistry
244 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.
Asymmetric nucleophilic catalysis with planar-chiral DMAP derivatives and chiral phosphines : synthetic and mechanistic studies
Thesis
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<Abstract>Chapter 1 describes the development and detailed mechanistic investigation of the first non-enzymatic method for the dynamic kinetic resolution of secondary alcohols via enantioselective acylation, with acetyl isopropyl carbonate, through the use of a planar-chiral DMAP derivative (an acylation catalyst) in combination with a ruthenium complex (an alcohol-racemization catalyst). Chapter 2 describes the development and detailed mechanistic investigation of the enantioselective synthesis of tertiary alkyl fluorides via the [alpha]-fluorination of ketenes catalyzed by a planar-chiral nucleophile with N-fluorodibenzenesulfonimide in the presence of sodium pentafluorophenoxide. Chapter 3 describes the development and preliminary mechanistic study of the first asymmetric, phosphine-catalyzed intramolecular [3 + 2] cycloadditions of allenes with alkenes that furnish an array of diastereomerically pure bicyclic compounds bearing two or three contiguous tertiary! quaternary stereocenters.</Abstract>
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