Alexandria Digital Research Library

I. Green chemistry and metathesis : II. Copper hydride 1,2- and 1,4-reductions of enones

Author:
Voigtritter, Karl Robert
Degree Grantor:
University of California, Santa Barbara. Chemistry
Degree Supervisor:
Bruce H. Lipshutz and Donald H. Aue
Place of Publication:
[Santa Barbara, Calif.]
Publisher:
University of California, Santa Barbara
Creation Date:
2013
Issued Date:
2013
Topics:
Chemistry, Inorganic, Chemistry, Organic, and Chemistry, General
Keywords:
DTF
Catalysis
Green Chemistry
Mechanism
Copper Hydride
Metathesis
Genres:
Online resources and Dissertations, Academic
Dissertation:
Ph.D.--University of California, Santa Barbara, 2013
Description:

As the chemical industry is becoming more conscious about the amount of hazardous waste they are generating, green chemistry and its underlying principles are becoming more relevant. One approach that can be taken to eliminate unnecessary waste would be to remove organic solvents from organic reactions. A second approach would be to use catalysis whenever possible. Research into both of these approaches is the focus of this thesis. Nonionic surfactants in water, namely the vitamin E based amphiphiles (PTS and the newly developed TPGS-750-M), have played important roles in enabling these two approaches. Numerous transition metal catalyzed transformations can now be accomplished in water at room temperature. The Lipshutz group's chemistry in water is an important advance in surfactant technology evidenced by its recent award of the EPA's Presidential Green Chemistry Challenge Award. This thesis will detail both cross- and ring-closing metathesis, Miyaura borylations, copper hydride-catalyzed asymmetric conjugate reductions, and copper(I)/TEMPO catalyzed oxidations. The copper hydride-catalyzed conjugate reduction has become a valuable and reliable method for generating a stereocenter beta to what was an beta,beta-unsaturated system. The method is mild, and in general, selective. Curiously, when alpha-substituted or acyclic beta,beta-disubstituted enones are subjected to the reduction conditions created when nonracemic DTBM-SEGPHOS is employed; reduction of the ketone, rather than the enone takes place. The newly formed alcohols are generated in high enantiomeric excesses. A mechanistic investigation was pursued using computational chemistry.

Physical Description:
1 online resource (361 pages)
Format:
Text
Collection(s):
UCSB electronic theses and dissertations
ARK:
ark:/48907/f33j3b3v
ISBN:
9781303732034
Catalog System Number:
990041153580203776
Rights:
Inc.icon only.dark In Copyright
Copyright Holder:
Karl Voigtritter
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