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Beak, Peter Curtis, Michael David 2015-09-25T22:14:44Z 2015-09-25T22:14:44Z 10000-01-01 2000 2000 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. Made available in DSpace on 2015-09-25T22:14:44Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 9989975.pdf: 7069377 bytes, checksum: 46447ca66bb4beed1d0cf18d2289e3ee (MD5) Previous issue date: 2000 Embargo set by: Seth Robbins for item 85760 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 179 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2000. http://hdl.handle.net/2142/84479 (MiAaPQ)AAI9989975 eng Chemistry, Organic (--)-Sparteine Mediated Asymmetric Synthesis Through Conjugate Addition of Allylic and Benzylic Organolithium Species: Development of a Methodology and Its Application Toward a Total Synthesis text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.