University of Illinois Urbana-Champaign

Fundamental and Applied Studies in Asymmetric Catalysis

Fields, Lisa Beattie

This item is only available for download by members of the University of Illinois community. Students, faculty, and staff at the U of I may log in with your NetID and password to view the item. If you are trying to access an Illinois-restricted dissertation or thesis, you can request a copy through your library's Inter-Library Loan office or purchase a copy directly from ProQuest.

Permalink

https://hdl.handle.net/2142/72290

Description

Title
Fundamental and Applied Studies in Asymmetric Catalysis
Author(s)
Fields, Lisa Beattie
Issue Date
1993
Doctoral Committee Chair(s)
Jacobsen, Eric N.
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
Abstract
  • In Part I of this thesis, a new class of optically active heterobimetallic complexes is described. The complexes L*MCl2 (M = Pt(II), Pd(II), L* = C2-symmetric boron containing bisphosphine ligand) and (Rh(cod)(L*)) ClO4 (cod = eta2,eta 2-1,5-cyclooctadiene) were synthesized as templates for asymmetric catalytic reactions that could involve substrate precoordination to a Lewis acidic site remote from the transition metal reaction site. Primary amines were found to bind reversibly via a nitrogen-boron interaction to the free ligands L*. 1H NMR measurements revealed that the binding constant of representative primary amines to L* could be tuned through variation of the electronic properties of the substituents covalently bound to boron.
  • In Part II, the asymmetric synthesis of S-(+)-ibuprofen is described. The key asymmetry-inducing step was the catalytic epoxidation of 4-isobutylstyrene using household bleach as the terminal oxidant and chloro- (S,S)-[(2,2 '-((1,2-diphenyl-1,2-ethanediyl)bis(nitrilomethylidyne)) bis (6-(1,1-dimethylethyl)-4-methylphenolato))-N,N ', O,O'] manganese(III) as the catalyst. Enantioselectivities in the range of 50-63% were obtained using this or similar catalysts. The final product was obtained from the epoxide via treatment with trimethylaluminum followed by KMnO 4 oxidation.
  • In Part III, the use of chiral Mn(III)salen complexes as asymmetric C-H activation catalysts for aryl alkanes was examined. Indanol was obtained from indan in 23% ee using household bleach as the terminal oxidant. Kinetic resolution of benzylic alcohols also occurred under reaction conditions, with enantioselectivities in the range of 2--20%.
Graduation Semester
1993
Type of Resource
text
Permalink
http://hdl.handle.net/2142/72290

Owning Collections

Graduate Dissertations and Theses at Illinois PRIMARY
Graduate Theses and Dissertations at Illinois
Dissertations and Theses - Chemistry