Ir(â…¢)&Rh(â…¢)-catalyzed Redox-neutral Functionalization Of Arenes Via C-H Activation

In recent years, Rh(Ⅲ) and Ir(Ⅲ) catalysts have been increasingly employed in C-H activation due to their high activity, high selectivity, broad scopes and functional-groups, as an efficient and atom-economic route in organic synthesis has been attracted more and more chemists’ attentions. This dissertation mainly focused on Rh(Ⅲ)-& Ir(Ⅲ) catalyzed coupling of arenes with strained rings by C-H activation, C-H nitration, C-H alkyn ylation, annulation with alkynes for construction of various cyclic compounds, and Ir(Ⅲ)-catalyzed C-H alkynylation of arenes. The results are as following:1. A reaction system was developed combining nitrogen compoundsand C-H activation of arenes, Under redox-neutral conditions.Using [IrCp*Cl2]2 as catalyst, adding CsOAc, water and ethanol as solvent, reaction at 100 ℃. The aromatic C-H activation and dehydration process, generate indoles product. The reaction conditions are relatively mild, the catalyst amount is small, water and ethanol as green solvent. And the mechanism is studied in detail, and the possible reaction mechanism is explored.2. Using the umpolung strategy, an approach of Rh(III)-catalyzed C-H activation of arenes coupling with nucleophilies was discovered. And C-H alkynylation of arenes was realized using TIPS-EBX as umpolung alkynylation reagent. It is found that Rh(Ⅲ) and Ir(Ⅲ) exhibited complementary substrate scope in C-H alkynylation.