Alexandria Digital Research Library

Novel reactivity and asymmetric transformations with nitroso compounds

Author:
Sandoval, David
Degree Grantor:
University of California, Santa Barbara. Chemistry
Degree Supervisor:
Javier Read de Alaniz
Place of Publication:
[Santa Barbara, Calif.]
Publisher:
University of California, Santa Barbara
Creation Date:
2015
Issued Date:
2015
Topics:
Organic chemistry
Keywords:
Ene
Aldol
Synergistic Catalysis
Nitroso
Electrophilic Amination
Genres:
Dissertations, Academic and Online resources
Dissertation:
Ph.D.--University of California, Santa Barbara, 2015
Description:

The development of efficient methods for the synthesis of highly functionalized chiral molecules is of great interest in organic chemistry. Given the ubiquity of nitrogen and oxygen containing compounds in nature and biologically relevant molecules, the direct asymmetric construction of C-N and C-O bonds becomes invaluable. While arylnitroso compounds are known sources of electrophilic nitrogen and oxygen, their use is inherently limited by their known toxicity and the difficulty of removing the N-aryl group for subsequent C-N bond forming reactions. Our group has focused on the use of nitrosocarbonyl intermediates which are generated in situ from substituted hydroxylamines and bear readily removable protecting groups on nitrogen. Nitrosocarbonyl intermediates are highly reactive and prone to decomposition using traditional stoichiometric oxidation processes. We postulated that the identification of a mild oxidation protocol would offer a marked improvement to known reaction platforms and facilitate the development of un-discovered synthetic transformations.

The context for developing nitrosocarbonyl chemistry will be provided through an overview of relevant nitroso compounds, with an emphasis on synthesis and reactivity. The discovery of the nitrosocarbonyl aldol reaction is a major component of this thesis, and this will be prefaced with a review on the state of the art in this area. The asymmetric nitroso ene reaction has long remained an elusive target in this area of research, and presented herein is an account of the first general asymmetric nitrosocarbonyl ene reaction, along with a proposed strategy to access enantioselective transformations with nitroso compounds.

Physical Description:
1 online resource (261 pages)
Format:
Text
Collection(s):
UCSB electronic theses and dissertations
ARK:
ark:/48907/f3q52mt0
ISBN:
9781339218588
Catalog System Number:
990045866010203776
Rights:
Inc.icon only.dark In Copyright
Copyright Holder:
David Sandoval
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