Date of Award

Summer 2005

Document Type

Dissertation - Restricted

Degree Name

Doctor of Philosophy (PhD)



First Advisor

Yi, Chae S.

Second Advisor

Haworth, Daniel T.

Third Advisor

Donaldson, William A.


Transition metal-catalyzed C-H bond activation reactions have been shown to be effective methods for the functionalization of unreactive hydrocarbons. Since Murai's pioneering report on ruthenium-catalyzed regioselective arene-to-alkene coupling reactions, a number of well-defined, late transition metal catalysts have been shown to mediate regioselective C-H bond activation of hydrocarbons, Recently, late metal complexes have also been found to catalyze the regioselective coupling reactions of nitrogen heterocycles and alkenes as well as sp3 C-H bond insertions and dehydrogenation of tertiary amines and ethers, Selective C-H bond activation of unprotected amines is especially desirable in organic synthesis due to the prevalent occurrence of nitrogen compounds in natural products and pharmaceutical agents. An efficient catalytic C-H bond activation/hydroarnination protocol has been developed for the synthesis for quinoline derivatives. A catalytically active cationic ruthenium-acetylide complex has been isolated and characterized. The normal isotope effect (kcH/kco = 2.5) and a highly negative Harnrnett p value are consistent with a mechanism involving onho-C-H bond activation rate-determining step, Efforts to establish a detailed mechanism as well as the role of ruthenium-acetylide species in amination reactions are currently underway.



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