Cobalt-catalyzed C-H functionalization: from mechanistic studies to synthetic methodologies

This Ph.D. dissertation describes the synthesis and characterization of bench-top stable aryl-Co(III) organometallic species using commercially available cobalt(II) salts and a macrocyclic model substrate. Special attention will be paid to the C-H activation step to elucidate the operating mechanism in the high-valent cobalt-mediated cleavage of C-H bonds. Mechanistic experiments, as well as spectroscopic characterization of intermediates will be useful to give light to a basic underdeveloped step in cobalt C-H activation methodologies. In addition, reactivity of the isolated aryl-Co(III) intermediates towards a variety of coupling partners will be tested. On one hand, annulation reaction using alkynes will be studied. On the other hand, cobalt-mediated insertion of metal-carbenoids into C-H bonds will be evaluated using ethyl diazoacetates. Moreover, both transformation will be extrapolated to substrates bearing an 8-aminoquinoline group in cobalt-catalyzed C-H functionalization methodologies with alkynes and alkyl nitrites for the synthesis of cyclic sulfonamide motifs and 5- and 7-nitro-8-aminoquinolines, respectively ​
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