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Title:Fundamental and Applied Studies in Asymmetric Catalysis
Author(s):Fields, Lisa Beattie
Doctoral Committee Chair(s):Jacobsen, Eric N.
Department / Program:Chemistry
Discipline:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(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%.
Issue Date:1993
Type:Text
Description:118 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1993.
URI:http://hdl.handle.net/2142/72290
Other Identifier(s):(UMI)AAI9411619
Date Available in IDEALS:2014-12-17
Date Deposited:1993


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