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Stereoselective addition of simple amines to unactivated alkenes
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TitleInfo
Title
Stereoselective addition of simple amines to unactivated alkenes
Name
(type = personal)
NamePart
(type = family)
Reznichenko
NamePart
(type = given)
Alexander
NamePart
(type = date)
1984-
DisplayForm
Alexander Reznichenko
Role
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(authority = RULIB)
author
Name
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Hultzsch
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Kai C.
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Kai C. Hultzsch
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Advisory Committee
Role
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chair
Name
(type = personal)
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(type = family)
Goldman
NamePart
(type = given)
Alan S
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Alan S Goldman
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Advisory Committee
Role
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(authority = RULIB)
internal member
Name
(type = personal)
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(type = family)
Seidel
NamePart
(type = given)
Daniel
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Daniel Seidel
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Advisory Committee
Role
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(authority = RULIB)
internal member
Name
(type = personal)
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(type = family)
Jaekle
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(type = given)
Frieder
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Frieder Jaekle
Affiliation
Advisory Committee
Role
RoleTerm
(authority = RULIB)
outside member
Name
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NamePart
Rutgers University
Role
RoleTerm
(authority = RULIB)
degree grantor
Name
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NamePart
Graduate School - New Brunswick
Role
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school
TypeOfResource
Text
Genre
(authority = marcgt)
theses
OriginInfo
DateCreated
(qualifier = exact)
2012
DateOther
(qualifier = exact);
(type = degree)
2012-10
Place
PlaceTerm
(type = code)
xx
Language
LanguageTerm
(authority = ISO639-2b);
(type = code)
eng
Subject
(authority = RUETD)
Topic
Chemistry and Chemical Biology
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TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier
(type = RULIB)
ETD
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ETD_4150
PhysicalDescription
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electronic resource
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application/pdf
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text/xml
Extent
xxii, 339 p. : ill.
Note
(type = degree)
Ph.D.
Note
(type = bibliography)
Includes bibliographical references
Note
(type = vita)
Includes vita
Note
(type = statement of responsibility)
by Alexander Reznichenko
Abstract
(type = abstract)
The facile and atom-economic synthesis of amines via direct addition of an amine
N–H or C–H moiety to an unactivated alkene belongs to the major challenges of
organometallic catalysis. In this thesis we summarize our efforts towards the
development of efficient stereoselective catalysts for the addition of the amine N–H-fragment to alkenes, which is known as a catalytic hydroamination reaction. We have performed a detailed mechanistic study of the rare earth metal-catalyzed stereoselective hydroamination/cyclization with particular focus on the kinetic resolution of racemic aminoalkenes. Key factors governing the reaction efficiency were determined and we were able to address the significantly more challenging intermolecular hydroamination by utilizing two rare earth metal-based catalyst families featuring sterically tunable C1- and C2-symmetric diolate ligand frameworks. The first example of an asymmetric intermolecular hydroamination of a simple alkene was demonstrated and enantioselectivities of up to 61% ee and 73% de were achieved in this novel catalytic process. Steric features of the voluminous silyl groups were shown to be detrimental for both catalyst stability and catalytic performance. A novel NOBIN-based C1-symmetric diolate ligand family was introduced and it was utilized for preparation of rare earth and group 4 metal diolates. Novel NOBIN-based complexes were active catalysts in hydroamination/cyclization reaching selectivities of up to 92% ee. We have also
addressed the problem of limited substrate scope of group 4 metal-based hydroamination catalysts by introducing novel zirconium bis(amidate) complexes which perform hydroamination/cyclization of challenging substrates, including aminoheptenes, under mild reaction conditions. In addition to our studies of a hydroamination reaction we have also addressed a complementary transformation which involves a C–H addition of an amine to an unactivated alkene and is known as a hydroaminoalkylation reaction. We have developed highly active and enantioselective (up to 98% ee) group 5 metal-based catalysts for this transformation using 3,3’disilylated binaphtholate ligands and for the
first time studied the kinetics and mechanism of the catalytic hydroaminoalkylation. The reaction was found to proceed via fast reversible non-dissociative metallaaziridine formation, followed by a fast alkene insertion and rate-determining amine exchange.
N–H or C–H moiety to an unactivated alkene belongs to the major challenges of
organometallic catalysis. In this thesis we summarize our efforts towards the
development of efficient stereoselective catalysts for the addition of the amine N–H-fragment to alkenes, which is known as a catalytic hydroamination reaction. We have performed a detailed mechanistic study of the rare earth metal-catalyzed stereoselective hydroamination/cyclization with particular focus on the kinetic resolution of racemic aminoalkenes. Key factors governing the reaction efficiency were determined and we were able to address the significantly more challenging intermolecular hydroamination by utilizing two rare earth metal-based catalyst families featuring sterically tunable C1- and C2-symmetric diolate ligand frameworks. The first example of an asymmetric intermolecular hydroamination of a simple alkene was demonstrated and enantioselectivities of up to 61% ee and 73% de were achieved in this novel catalytic process. Steric features of the voluminous silyl groups were shown to be detrimental for both catalyst stability and catalytic performance. A novel NOBIN-based C1-symmetric diolate ligand family was introduced and it was utilized for preparation of rare earth and group 4 metal diolates. Novel NOBIN-based complexes were active catalysts in hydroamination/cyclization reaching selectivities of up to 92% ee. We have also
addressed the problem of limited substrate scope of group 4 metal-based hydroamination catalysts by introducing novel zirconium bis(amidate) complexes which perform hydroamination/cyclization of challenging substrates, including aminoheptenes, under mild reaction conditions. In addition to our studies of a hydroamination reaction we have also addressed a complementary transformation which involves a C–H addition of an amine to an unactivated alkene and is known as a hydroaminoalkylation reaction. We have developed highly active and enantioselective (up to 98% ee) group 5 metal-based catalysts for this transformation using 3,3’disilylated binaphtholate ligands and for the
first time studied the kinetics and mechanism of the catalytic hydroaminoalkylation. The reaction was found to proceed via fast reversible non-dissociative metallaaziridine formation, followed by a fast alkene insertion and rate-determining amine exchange.
Subject
(authority = ETD-LCSH)
Topic
Amines--Synthesis
Subject
(authority = ETD-LCSH)
Topic
Catalysts
Identifier
(type = hdl)
http://hdl.rutgers.edu/1782.1/rucore10001600001.ETD.000066957
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TitleInfo
Title
Graduate School - New Brunswick Electronic Theses and Dissertations
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rucore19991600001
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(displayLabel = Rutgers, The State University of New Jersey)
NjNbRU
Identifier
(type = doi)
doi:10.7282/T3DZ0728
Genre
(authority = ExL-Esploro)
ETD doctoral
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Rights
RightsDeclaration
(ID = rulibRdec0006)
The author owns the copyright to this work.
RightsHolder
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Name
FamilyName
Reznichenko
GivenName
Alexander
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime
(encoding = w3cdtf);
(qualifier = exact);
(point = start)
2012-06-14 00:01:59
AssociatedEntity
Name
Alexander Reznichenko
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.
Copyright
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Copyright protected
Availability
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Open
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Permission or license
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