Asymmetric nucleophilic catalysis with planar-chiral DMAP derivatives and chiral phosphines : synthetic and mechanistic studies
Author(s)Lee, Sarah Yunmi
Massachusetts Institute of Technology. Department of Chemistry.
Gregory C. Fu.
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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.
Thesis: Ph. D. in Organic Chemistry, Massachusetts Institute of Technology, Department of Chemistry, 2014.Cataloged from PDF version of thesis. Vita.Includes bibliographical references.
DepartmentMassachusetts Institute of Technology. Department of Chemistry.; Massachusetts Institute of Technology. Department of Chemistry
Massachusetts Institute of Technology