University of Illinois Urbana-Champaign

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

Pippel, Daniel James

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Description

Title
Chiral Homoenolate Synthetic Equivalents: Mechanistic, Structural, and Kinetic Investigations
Author(s)
Pippel, Daniel James
Issue Date
2000
Doctoral Committee Chair(s)
Beak, Peter
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Language
eng
Abstract
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.
Graduation Semester
2000
Type of Resource
text
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http://hdl.handle.net/2142/84493

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