Asymmetric nucleophilic catalysis with planar-chiral DMAP derivatives and chiral phosphines : synthetic and mechanistic studies
Name
899242342-MIT.pdf
Description
Full printable version
Size
21.99 MB
Format
Adobe PDF
Checksum (MD5)
8ecd329c9469fcfce187f723e8ed9eb9
Author(s)
Lee, Sarah Yunmi
Advisor(s)
Gregory C. Fu.
Date Issued
2014
Publisher
Massachusetts Institute of Technology
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.
Description
Thesis: Ph. D. in Organic Chemistry, Massachusetts Institute of Technology, Department of Chemistry, 2014.
Cataloged from PDF version of thesis. Vita.
Includes bibliographical references.
Subjects
Chemistry.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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