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Development of tetraphosphorus ligands and their applications in olefin hydroformylation

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Title
Development of tetraphosphorus ligands and their applications in olefin hydroformylation
Name (type = personal)
NamePart (type = family)
Cai
NamePart (type = given)
Chaoxian
NamePart (type = date)
1968-
DisplayForm
Chaoxian Cai
Role
RoleTerm (authority = RULIB)
author
Name (type = personal)
NamePart (type = family)
Zhang
NamePart (type = given)
Xumu
DisplayForm
Xumu Zhang
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
chair
Name (type = personal)
NamePart (type = family)
Kimball
NamePart (type = given)
David
DisplayForm
David Kimball
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
internal member
Name (type = personal)
NamePart (type = family)
Hu
NamePart (type = given)
Longqin
DisplayForm
Longqin Hu
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
internal member
Name (type = personal)
NamePart (type = family)
Hultzsch
NamePart (type = given)
Kai
DisplayForm
Kai Hultzsch
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)
2012
DateOther (qualifier = exact); (type = degree)
2012-05
Place
PlaceTerm (type = code)
xx
Language
LanguageTerm (authority = ISO639-2b); (type = code)
eng
Abstract (type = abstract)
In Chapter 1, a general introduction to the reaction of rhodium-catalyzed hydroformylation of olefins is presented with its broad utility in organic synthesis, reaction mechanism, and a brief review of the current advances in ligand development. In Chapter 2, new tetraphosphoramidite ligands have been designed and synthesized. These ligands have been applied in the rhodium-catalyzed regioselective hydroformylation of various functionalized allyl, vinyl, and styrene derivatives. Remarkable high linear selectivity was obtained. The rhodium/tetraphosphoramidite catalyst system is highly effective to produce linear aldehydes from functionalized allyl derivatives with substituents containing heteroatoms such as O, N, Si and halogens either directly adjacent to or at distance to the allyl group. For vinyl derivatives, the ligand is highly linear selective for acrylic derivatives, styrene, vinyl pyridines and vinyl phthalimide. The catalyst system makes it possible to prepare Cn (n ≥ 3) functionalized terminal aldehydes from readily available vinyl and allyl derivatives by hydroformylation with high linear selectivity and efficiency. The electronic effects on catalyst activity and regioselectivity by both ligands and styrene derivatives have been studied with Hammett plots. For the substituent changes in ligands, with the increase of Hammett constant σp, the linear selectivity increases but the catalyst activity decreases. For the substituent changes in styrenes, with the increase of σp, the linear selectivity decreases but the catalyst activity increases. In Chapter 3, new class of tetraphosphine ligands has been developed and applied in the rhodium-catalyzed regioselective hydroformylation of terminal and internal olefins. The steric and electronic effects of substituents on tetraphosphine have also been studied. The high linear selectivity (above 97% for 1-octene and 1-hexene) at high temperature (140 oC) showing by those tetraphosphine ligands is remarkable considering the commonly observed low linear selectivity under similar reaction conditions when bisphosphine analogues were used. The rhodium/tetraphosphine catalyst system is also highly effective for the isomerization and hydroformylation of 2-alkenes to form linear aldehydes. Greater than 95% linear selectivity and up to 94% yield of the total aldehydes were obtained for 2-pentene, 2-hexene and 2-octene.
Subject (authority = RUETD)
Topic
Medicinal Chemistry
RelatedItem (type = host)
TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_3881
PhysicalDescription
Form (authority = gmd)
electronic resource
InternetMediaType
application/pdf
InternetMediaType
text/xml
Extent
xii, 138 p. : ill.
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
Note (type = general note)
Includes vita
Note (type = statement of responsibility)
by Chaoxian Cai
Subject (authority = ETD-LCSH)
Topic
Hydroformylation
Subject (authority = ETD-LCSH)
Topic
Alkenes
Subject (authority = ETD-LCSH)
Topic
Ligands (Biochemistry)
Identifier (type = hdl)
http://hdl.rutgers.edu/1782.1/rucore10001600001.ETD.000065089
RelatedItem (type = host)
TitleInfo
Title
Graduate School - New Brunswick Electronic Theses and Dissertations
Identifier (type = local)
rucore19991600001
Location
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NjNbRU
Identifier (type = doi)
doi:10.7282/T3NS0SVN
Genre (authority = ExL-Esploro)
ETD doctoral
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Rights

RightsDeclaration (ID = rulibRdec0006)
The author owns the copyright to this work.
RightsHolder (type = personal)
Name
FamilyName
Cai
GivenName
Chaoxian
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2012-04-09 13:54:40
AssociatedEntity
Name
Chaoxian Cai
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)
2012-05-31
DateTime (encoding = w3cdtf); (qualifier = exact); (point = end)
2014-05-31
Type
Embargo
Detail
Access to this PDF has been restricted at the author's request. It will be publicly available after May 31st, 2014.
Copyright
Status
Copyright protected
Availability
Status
Open
Reason
Permission or license
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