Rh(Ⅲ)-Catalyzed C-H Bond Functionalization Reactions

Transition metal catalyzed C-H bond activation has emerged as a powerful and atom-economical strategy for the organic synthesis. For a very long time, the research of this area was focus on the development and application of Pd catalyst. However, more and more chemists switch their interests to other alternatives, such as Ni, Ru and Rh. Specifically, Rhodium catalyst was the most striking, for its high catalytic activity, low catalyst loading and mild reaction condition. Considering these qualities, our research also focused on the Rh-catalyzed C-H functionalization reaction. The main contents of this thesis was summarize as follows:1. Introduction:The history and development of Rh(Ⅲ) catalyst system. We present the beginning, development and current situation of this research area. Meanwhile, with categories, we systematically described the research achievement of this area.2. Rh/Ag-catalyzed nitrile assisted C-H bond oxidative Heck reaction. For the first time, we have employed nitrile to assist the Rh/Ag-catalyzed ortho C-H activation. Nitrile was widespread contained in organic compounds, which can easily transfer to imine in suitable condition. Taking advantage of this property, we succeed obtained amide derivatives from nitriles directly in one-pot reaction by the Rh(Ⅲ)-catalyzed ortho C-H bond oxidative Heck reaction.3. Rh-catalyzed divergent functionalization of indoles. We have introduced acryloyl silanes into the Rh-catalyzed C-H functionalization reactions for the first time, which developed a novel way for the synthesis of acyl silanes. Unexpectedly, we have achieved excellent chemo-selectivity in this reaction, which delivered hydroarylation product and alkenylation product respectively. Furthermore, poly-cyclic indole derivatives were easily accessed from2-alkenylation products through visible-light-induced6-n electrocyclization reaction.