Rh(Ⅲ)-catalyzed N-amino-directed C-H Bond Activation And Synthesis Of Naphthalenes Based On The Coupling Of Enaminones With Either Alkynes Or α-diazo-β-ketoesters

In recent years, as a result of atom and step-economic and the diversity of the reaction, the transition metal-catalyzed C-H bond activation has made great progress. In the first chapter, some researches on the activation of Rh catalyzed C-H bond activation were described.In the second chapter, we study Rh(III)-catalyzed, N-amino-directed C-H alkenylation generates either olefination products or indoles in a atom and step-economic manner at room temperature. At first we commenced our inerstigation by screening experimental condations for N-amino-directed C-H olefination reaction. Then the scope of the reaction was examined under standard reaction condition. With olefination products in hand, we next performed heterocycle synthesis. Then we slao examined the reation for alkenes, after this we have completed a series of mechanism experiments, such as deuterium exchange experiments, in combination with competition and kinetic isotope experiments, suggest rate-limiting C-H activation and N-N bond cleavage/internal oxidation mechanism for the C-H alkenylation reaction. We also completed the experience of synthesis and characterization of Rh(Ⅲ) intermediates, the relationship between the valence of Rh in catalytic cycle, internal oxidation and H", thus, we proposed a reasonable reaction mechanism.At last, we study the Rh(Ⅲ)-catalyzed synthesis of naphthalenes, based on the coupling of enaminones with either alkynes or alpha-diazo-beta-ketoesters. Two reactive functionalities (hydroxyl and aldehyde) are streamlined into the newly formed cyclic framework and a broad range of substituents are tolerated, rendering target products readily available for further synthetic elaboration, we commenced our inerstigation by screening experimental condations. Then the scope of the reaction was examined. With the satisfactory results obtained for alkyne substrates, we envisioned that alpha-diazo-beta-ketoester might serve equally well as a competent coupling partner, we got well scope of the reaction. After this we have completed a series of mechanism experiments. Based on the above experimental results and literature precedents, two plausible mechanism are proposed.