(--)-Sparteine Mediated Asymmetric Synthesis Through Conjugate Addition of Allylic and Benzylic Organolithium Species: Development of a Methodology and Its Application Toward a Total Synthesis

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.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Curtis, Michael David

Contributors dc:contributor

• Beak, Peter

• Chemistry, Organic

Language dc:language

eng

Identifier

(MiAaPQ)AAI9989975

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84479