Copper Catalyzed C-C, C-H Bond Cleavage/Transformation

Carbon-carbon single bond and carbon-hydrogen bond are the prevalence of twotypes of chemical bond in organic molecules. The cleavage/translation of C C andC H bonds has great significance in organic chemistry and chemical industry,especially in the use of petroleum feedstock. Because of the inertness and diversity ofC C and C H bonds, selective activation of these bonds remains one of the mostchallenging topics in organic chemistry field. Over the last years, constructing acarbon carbon/carbon heteroatom via C H bond activation fascinates organicchemists, which became the frontier domains in organic chemistry research. However,the cleavage/translation of C C bond reported relatively less. The noble metalcatalyzed C C and C H selective cleavage have absolute predominance duringreported literatures. Therefore, the development of inexpensive and green catalystsystem to realize selective activation/functionalization of C C and C H bonds hasimportant research significance.Copper/dioxygen system shows good catalytic and oxidation ability in organicreactions, copper salt as a catalyst possesses the advantages of inexpensive, easyavailable and less pollution to the environment, molecular oxygen is the ideal oxidantbecause of its abundance, low cost and lack of toxic by-products. Thus,copper/dioxygen system accords with the aim of green chemistry.The thesis developed a strategy to realize cleavage/translation of inert C C andC H bonds via copper/dioxygen system. Mainly includes the following aspects:1. This dissertation developed a new strategy of demethylation of methyl ketones byusing copper salt and dioxygen as catalyst and oxidant, which realized chemoselectiveoxidative C(CO) C(methyl) bond cleavage of methyl ketones. This research is animportant breakthrough in aliphatic C C bond fracture.2. Transition-metal-catalyzed carbon carbon bond activation has attracted muchattention in the past years, but the nitration of C H bond has rarely reported. We have developed a novel copper-mediated chelation-assisted ortho C H nitration of(hetero)-arenes using dioxygen as a terminal oxidant.