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Stereoselective addition of simple amines to unactivated alkenes
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Reznichenko, Alexander. Stereoselective addition of simple amines to unactivated alkenes. Retrieved from https://doi.org/doi:10.7282/T3DZ0728

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TitleStereoselective addition of simple amines to unactivated alkenes
NameReznichenko, Alexander (author); Hultzsch, Kai C. (chair); Goldman, Alan S (internal member); Seidel, Daniel (internal member); Jaekle, Frieder (outside member); Rutgers University; Graduate School - New Brunswick
Date Created2012
Other Date2012-10 (degree)
SubjectChemistry and Chemical Biology, Amines--Synthesis, Catalysts
Extentxxii, 339 p. : ill.
DescriptionThe 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.
NotePh.D.
NoteIncludes bibliographical references
NoteIncludes vita
Noteby Alexander Reznichenko
Genretheses, ETD doctoral
Persistent URLhttps://doi.org/doi:10.7282/T3DZ0728
Languageeng
CollectionGraduate School - New Brunswick Electronic Theses and Dissertations
Organization NameRutgers, The State University of New Jersey
RightsThe author owns the copyright to this work.
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