RUcore: Rutgers University Community Repository
Carbon-carbon fragmentation : history and new applications in complex terpene synthesis
Descriptive
TitleInfo
Title
Carbon-carbon fragmentation : history and new applications in complex terpene synthesis
Name
(type = personal)
NamePart
(type = family)
Drahl
NamePart
(type = given)
Michael A.
NamePart
(type = date)
1986-
DisplayForm
Michael Drahl
Role
RoleTerm
(authority = RULIB)
author
Name
(type = personal)
NamePart
(type = family)
Williams
NamePart
(type = given)
Lawrence J.
DisplayForm
Lawrence J. Williams
Affiliation
Advisory Committee
Role
RoleTerm
(authority = RULIB)
chair
Name
(type = personal)
NamePart
(type = family)
Jones
NamePart
(type = given)
Roger A.
DisplayForm
Roger A. Jones
Affiliation
Advisory Committee
Role
RoleTerm
(authority = RULIB)
internal member
Name
(type = personal)
NamePart
(type = family)
Warmuth
NamePart
(type = given)
Ralf
DisplayForm
Ralf Warmuth
Affiliation
Advisory Committee
Role
RoleTerm
(authority = RULIB)
internal member
Name
(type = personal)
NamePart
(type = family)
Johnson
NamePart
(type = given)
James A.
DisplayForm
James A. Johnson
Affiliation
Advisory Committee
Role
RoleTerm
(authority = RULIB)
outside member
Name
(type = corporate)
NamePart
Rutgers University
Role
RoleTerm
(authority = RULIB)
degree grantor
Name
(type = corporate)
NamePart
Graduate School - New Brunswick
Role
RoleTerm
(authority = RULIB)
school
TypeOfResource
Text
Genre
(authority = marcgt)
theses
OriginInfo
DateCreated
(qualifier = exact)
2013
DateOther
(qualifier = exact);
(type = degree)
2013-10
Place
PlaceTerm
(type = code)
xx
Language
LanguageTerm
(authority = ISO639-2b);
(type = code)
eng
Abstract
(type = abstract)
C-C fragmentation is both powerful and elegant. Capable of stereospecifically introducing sp1-sp1, sp2-sp2, and sp2-sp-sp2 bond connectivity, it is the key transformation that allows all of the chemistry described herein. This dissertation begins with a comprehensive review of C-C fragmentation, which notably uncovers the lost origins of this transformation. Extensions of its utility in complex terpene synthesis are presented next. An integrated routing strategy was realized in the divergent enantioselective synthesis of the core ring systems of the xeniolide, xenibellol, and florlide natural products. A more general synthetic route was developed to gain direct access to the previously restricted, diverse, semi-validated structure space of the xenicane superfamily, and more than forty xenicane congeners were synthesized. These include xeniolides, blumiolides, florlides, bridgehead olefins and epoxides, keto-enol tautomeric mixtures, and the deshydroxymethyl xeniolide framework. Several other terpene motifs were also prepared, including functionalized cyclopentanones, CD ring systems of 18-methoxy-18-oxo-17-ketosteroids, and nine-membered ring-opening products. Seven of these novel compounds were found to selectively induce Bak- and Bax-dependent apoptosis in precancerous immortalized baby mouse kidney epithelial cells.
Subject
(authority = RUETD)
Topic
Chemistry and Chemical Biology
Subject
(authority = local)
Topic
Total synthesis
Subject
(authority = local)
Topic
Synthetic methods
Subject
(authority = local)
Topic
Diterpene
Subject
(authority = local)
Topic
Biosynthesis
Subject
(authority = local)
Topic
Transannular
Subject
(authority = local)
Topic
Anticancer
Subject
(authority = ETD-LCSH)
Topic
Terpenes--Synthesis
Subject
(authority = ETD-LCSH)
Topic
Fragmentation reactions
Subject
(authority = ETD-LCSH)
Topic
Carbon composites
Subject
(authority = ETD-LCSH)
Topic
Carbon--Synthesis
RelatedItem
(type = host)
TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier
(type = RULIB)
ETD
RelatedItem
(type = host)
TitleInfo
Title
Graduate School - New Brunswick Electronic Theses and Dissertations
Identifier
(type = local)
rucore19991600001
Identifier
ETD_5083
Identifier
(type = doi)
doi:10.7282/T3NZ85PQ
PhysicalDescription
Form
(authority = gmd)
electronic resource
InternetMediaType
application/pdf
InternetMediaType
text/xml
Extent
xx, 768 p. : ill.
Note
(type = degree)
Ph.D.
Note
(type = bibliography)
Includes bibliographical references
Note
(type = vita)
Includes vita
Note
(type = statement of responsibility)
by Michael A. Drahl
Location
PhysicalLocation
(authority = marcorg);
(displayLabel = Rutgers, The State University of New Jersey)
NjNbRU
Genre
(authority = ExL-Esploro)
ETD doctoral
Back to the top
Rights
RightsDeclaration
(ID = rulibRdec0006)
The author owns the copyright to this work.
RightsHolder
(type = personal)
Name
FamilyName
Drahl
GivenName
Michael
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime
(encoding = w3cdtf);
(qualifier = exact);
(point = start)
2013-09-30 14:17:21
AssociatedEntity
Name
Michael Drahl
Role
Copyright holder
Affiliation
Rutgers University. Graduate School - New Brunswick
AssociatedObject
Type
License
Name
Author Agreement License
Detail
I hereby grant to the Rutgers University Libraries and to my school the non-exclusive right to archive, reproduce and distribute my thesis or dissertation, in whole or in part, and/or my abstract, in whole or in part, in and from an electronic format, subject to the release date subsequently stipulated in this submittal form and approved by my school. I represent and stipulate that the thesis or dissertation and its abstract are my original work, that they do not infringe or violate any rights of others, and that I make these grants as the sole owner of the rights to my thesis or dissertation and its abstract. I represent that I have obtained written permissions, when necessary, from the owner(s) of each third party copyrighted matter to be included in my thesis or dissertation and will supply copies of such upon request by my school. I acknowledge that RU ETD and my school will not distribute my thesis or dissertation or its abstract if, in their reasonable judgment, they believe all such rights have not been secured. I acknowledge that I retain ownership rights to the copyright of my work. I also retain the right to use all or part of this thesis or dissertation in future works, such as articles or books.
RightsEvent
DateTime
(encoding = w3cdtf);
(qualifier = exact);
(point = start)
2013-10-31
DateTime
(encoding = w3cdtf);
(qualifier = exact);
(point = end)
2015-10-31
Type
Embargo
Detail
Access to this PDF has been restricted at the author's request. It will be publicly available after October 31st, 2015.
Copyright
Status
Copyright protected
Availability
Status
Open
Reason
Permission or license
Back to the top
Technical
RULTechMD
(ID = TECHNICAL1)
ContentModel
ETD
OperatingSystem
(VERSION = 5.1)
windows xp
Back to the top
Statistical Profile