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dc.contributor.authorTaban, Keivan
dc.date.accessioned2012-11-07T19:28:55Z
dc.date.available2012-11-07T19:28:55Z
dc.date.issued2012-11-07
dc.identifier.urihttp://hdl.handle.net/10464/4135
dc.description.abstractThe natural abundance of the N-heterocycle containing compounds has pushed the synthetic community toward the invention of new synthetic methods that result in the structural diversity of N-heterocycles. Among this, is the efficient and highly selective diamine mediated asymmetric lithiation process. Amongst the diamine chiral ligands, (-)-sparterine, which is a naturally occurring alkaloid proved to be an efficient one. Many successful, good yielding and highly selective lithiation reactions have been accomplished with the mediation by this chiral diamine base. Although, there are some examples of experimental and theoretical mechanistic studies in the literature, there is a lack of detailed understanding as to how it exactly induces the chirality. In this thesis is described a systematic investigation of how (-)-sparteine influences the stereoselectivity in the course of asymmetric lithiation reaction. This led us to the establishment of the function of A-ring’s β-CH2 effect and D-ring effect. Consequently, the importance of the A-ring and D-ring portions of (-)-sparteine in the stereoselectivity is unraveled. Another part of this thesis deals with the asymmetric lithiation of BF3-activated N,N- dimethylaminoferrocene in the presence of (1R, 2R)-N1,N2-bis(3,3-dimethylbutyl)-N1,N2-dimethylcyclohexane-1,2-diamine ( a (R,R)-TMCDA surrogate) with i-PrLi. Computational findings were in full accord with the experimental observations. Subsequently, the theoretically provided insights into the mechanism of the reaction were exploited in computational design of a new ligand. Unfortunately, the outcome of this design was not experimentally robust and an updated approach towards a successful design was explained.en_US
dc.language.isoengen_US
dc.publisherBrock Universityen_US
dc.subjectAsymmetric Lithiationen_US
dc.subjectN-heterocyclesen_US
dc.subjectTheoretical Studiesen_US
dc.titleUnderstanding the Origin of Selectivity in the Asymmetric Lithiation Reaction of N-Heterocycles: A Theoretical Studyen_US
dc.typeElectronic Thesis or Dissertationen_US
dc.degree.nameM.Sc. Chemistryen_US
dc.degree.levelMastersen_US
dc.contributor.departmentDepartment of Chemistryen_US
dc.degree.disciplineFaculty of Mathematics and Scienceen_US
dc.embargo.termsNoneen_US


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