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Title:(--)-Sparteine Mediated Asymmetric Synthesis Through Conjugate Addition of Allylic and Benzylic Organolithium Species: Development of a Methodology and Its Application Toward a Total Synthesis
Author(s):Curtis, Michael David
Doctoral Committee Chair(s):Beak, Peter
Department / Program:Chemistry
Discipline:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):Chemistry, Organic
Abstract:The synthetic utility of the methodology is demonstrated with the synthesis of diastereo-, and enantiomerically pure 2,3,4-trisubstituted gamma-lactams in high yield. In addition, conjugate addition of the allylic organolithium species with N-protected 4-pyridones provides high yields of the corresponding 1,4-addition adduct with high enantiomeric ratios (ers). The reaction is believed to proceed through an N-acyl pyridinium salt formed on reaction of N-protected pyridone with TMSCl. An organolithium species derived from N-Boc-N-( p-Methoxyphenyl)dimethylphenylsilyl-allylamine, stabilized with a silyl group rather than a phenyl, has been successfully employed in this lithiation-conjugate addition sequence. The enantioenriched products that arise on electrophilic substitution with N-protected pyridones are precursors to piperidine alkaloids. Moreover, this reaction has been applied as the key step in the total synthesis of an immediate precursor to the indolizidine alkaloid castanospermine.
Issue Date:2000
Type:Text
Language:English
Description:179 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2000.
URI:http://hdl.handle.net/2142/84479
Other Identifier(s):(MiAaPQ)AAI9989975
Date Available in IDEALS:2015-09-25
Date Deposited:2000


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