Beta-diketiminato copper complexes in C-H bond amination
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Thesis (M.S.)--Georgetown University, 2010.; Includes bibliographical references.; Text (Electronic thesis) in PDF format. The reactivity of beta-diketiminato copper oxo, copper hydroxide and copper acetate, [Br3NN]Cu(O2CMe), complexes towards oxidative C-H bond amination has been investigated. The complexes were reacted with aryl amines in neat C-H substrate. The copper oxo decomposes to the copper hydroxide which was found to be the active species in C-H amination. Ancillary ligand modifications are required to disfavor the copper hydroxide dimer and thus enhance its reactivity. The copper acetate was also found to be active in C-H amination which makes it an attractive candidate for a precatalyst in the [Cl2NN]Cu catalyzed C-H amination with unactivated amines.; The reactivity of beta-diketiminato copper(I) complexes, [Cl2NN]Cu and [Cl2NNCF3]Cu, towards C-H bond amidation has been investigated. [Cl2NN]Cu is protonated by organic amides and hence is unsuitable for catalysis. We found that the electron deficient [Cl2NNCF3] is a C-H amidation catalyst. Catalytic C-H amidation is achieved employing simple organic amides along with environmentally friendly di-tert-butylperoxide oxidant in the presence of 10 mol % [Cl2NNCF3] in neat C-H substrate. Further studies are required to find a suitable solvent for the reaction.
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http://hdl.handle.net/10822/552874Date Published
2010Subject
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Georgetown University
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Beta-Diketiminato Copper Complexes for C-H Bond Functionalization
(Georgetown University, 2014)C-H amination is an attractive methodology for constructing C-N bonds from seemingly unreactive C-H bonds. This process reduces group manipulations and reaction by-products. C-H amination catalysts are usually rhodium and ...
