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Lithium diamidobinaphthyl catalysts for asymmetric hydroamination

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Title
Lithium diamidobinaphthyl catalysts for asymmetric hydroamination
Name (type = personal)
NamePart (type = family)
Hurd
NamePart (type = given)
Lisa
DisplayForm
Lisa Hurd
Role
RoleTerm (authority = RULIB)
author
Name (type = personal)
NamePart (type = family)
Hultzsch
NamePart (type = given)
Kai Carsten
DisplayForm
Kai Carsten Hultzsch
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
chair
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)
Romsted
NamePart (type = given)
Laurence
DisplayForm
Laurence Romsted
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
internal member
Name (type = personal)
NamePart (type = family)
Hu
NamePart (type = given)
Longquin
DisplayForm
Longquin Hu
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)
Lithium catalyzed intramolecular hydroamination of unactivated alkenes has been known for over 20 years, although growth in this field has been limited. Deduction of structure activity relationships for these systems is a challenge because of their complex solution behavior. A series of axially chiral C2-symmetric diamidobinaphtyl dilithium salts given by the formula [{C10H6N(CH2CH2X)}2Li2]n where n = 2, 6 for X = NMe2, n = 2 for X = OMe, and n = 1 for X = NEt2 or N(CH2)5 were synthesized. Solid state characterization of these dilithium salts free of outside donor solvents allowed ligands to direct aggregation based on their steric hindrance and flexibility. All complexes showed π interactions between lithium and the naphthyl rings playing a significant role in the stabilization of the metal center. The complexes based on the sterically least demanding N-dimethyl-substituted ligand [{C10H6N(CH2CH2NMe2)}2Li2]n crystallize as a dimer in enantiopure form and as a hexameric cycle in racemic form. When used in combination with excess LiCH2SiMe3 various gem-dialkyl substituted aminopentenes were cyclized in up to 67% ee at 22°C. Cyclization of aminopentene at 40°C was also performed producing 2-methylpyrrolidine in up to 64% ee. The precatalysts were studied using DOSY, 7Li and variable temperature NMR spectroscopy. DOSY NMR spectroscopy suggests that solutions of (rac)-64 and (R)-64 exist as a mixture of monomers and dimers at 25°C, while (R)-65 and (R)-66 are monomeric. Addition of one equivalent LiCH2SiMe3 to (R)-64 resulted in a sharpening of 1H NMR spectra and produced a single peak in the 7Li NMR spectra, suggesting the formation of a new mixed aggregate, (R)-69. Kinetic studies for the cyclization of C-(1-allyl-cyclohexyl)-methylamine demonstrated a first order rate dependence on substrate and catalyst concentrations. A first order rate dependence on LiCH2SiMe3 was also observed, with enantioselectivity decreasing linearly as the concentration of LiCH2SiMe3 was increased. (R)-70 is a general representation of components found in the rate limiting transition state for the hydroamination/cyclization of C-(1-allyl-cyclohexyl)-methylamine. Solid state characterization of (R)-64 with two equivalents of 3-methyl-2-aza-spiro[4.5]decane bound to it revealed the formation of a monomeric species, (R)-68.
Subject (authority = RUETD)
Topic
Chemistry and Chemical Biology
RelatedItem (type = host)
TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_4967
PhysicalDescription
Form (authority = gmd)
electronic resource
InternetMediaType
application/pdf
InternetMediaType
text/xml
Extent
xxiii, 191 p. : ill.
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
Note (type = statement of responsibility)
by Lisa Hurd
Subject (authority = ETD-LCSH)
Topic
Lithium--Synthesis
Subject (authority = ETD-LCSH)
Topic
Chemical tests and reagents
RelatedItem (type = host)
TitleInfo
Title
Graduate School - New Brunswick Electronic Theses and Dissertations
Identifier (type = local)
rucore19991600001
Location
PhysicalLocation (authority = marcorg); (displayLabel = Rutgers, The State University of New Jersey)
NjNbRU
Identifier (type = doi)
doi:10.7282/T3DB7ZVQ
Genre (authority = ExL-Esploro)
ETD doctoral
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RightsDeclaration (ID = rulibRdec0006)
The author owns the copyright to this work.
RightsHolder (type = personal)
Name
FamilyName
Hurd
GivenName
Lisa
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2013-08-29 12:16:58
AssociatedEntity
Name
Lisa Hurd
Role
Copyright holder
Affiliation
Rutgers University. Graduate School - New Brunswick
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Type
License
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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)
2014-10-31
Type
Embargo
Detail
Access to this PDF has been restricted at the author's request. It will be publicly available after October 31st, 2014.
Copyright
Status
Copyright protected
Availability
Status
Open
Reason
Permission or license
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ETD
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