Chiral Homoenolate Synthetic Equivalents: Mechanistic, Structural, and Kinetic Investigations

The lithiation of N-Boc-N-( p-methoxyphenyl)-3-cyclohexylallylamine by n-BuLi/(-)-sparteine was examined kinetically by means of in situ infrared spectroscopy. The reaction is first order in allylic amine and zero-order in 1:1 base/ligand complex. When the relative concentrations of n-BuLi and (-)-sparteine are not held constant, the reaction exhibits an inverse dependence on n-BuLi concentration. The experimental results are rationalized by a generalized mechanism that is consistent with thermodynamic parameters, an extremely high isotope effect, and computer simulations.

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

• Pippel, Daniel James

Contributors dc:contributor

• Beak, Peter

• Chemistry, Organic

Language dc:language

eng

Identifier

(MiAaPQ)AAI9990108

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84493