Transition-metal Catalyzed Small Organic Molecule C-H Bond Hydroxylation And C-C Bond Cleavage

The transition-metal catalyzed C-H bond activation and C-C bond cleavage reaction is a hotspot in modern organic synthesis. The application of transition-metal catalzed small organic molecules C-H bond activation and C-C bond cleavage position selective and stereoselective activations not only contribute to the theory of organic chemistry development, but also contribute to the chemical industry application. This thesis developed a Cu catalyzed C-H bond hydroxylation reaction on the basis of S-containing groups directed thiophenols C-H bond hydroxylation/C-S bond coupling reaction. This thesis also developed a new Rh-catalyzed aromatic ketones direct C-C bond cleavage reaction.This paper first constructed a CuI-catalyzed C-H bond hydroxylation/C-S key coupling reaction. Apply this method was realized two new reactions:application enaminoketone as a ligand, CS2CO3as alkali, DMSO as reaction solvent, employed CuI catalyzed substituted thiophenol and halogenated benzene synthesis for the2-phenylthiophenols; employed substituted thiophenol and halogenated styrene as starting materials syntheted to2-styrenethiophenols. Employed ESI-MS mass spectrometry combined with DFT theoretical calculations to investigate the Cu-catalyzed C-H bond hydroxylation/C-S coupling reaction mechanism. ESI-MS mass spectrometry was used to capture the key intermediate quality informations and DFT theoretical calculations demonstrated possible reaction mechanism from thermodynamics and kinetics.This paper also developed a new Ag2O promote Rh catalyzed aromatic ketones direct C-C bond cleavage reaction. In this reaction, acetophenone and2-bromoacetophenone C-C bond were smoothly cut under mild conditions. The reaction was efficiently syntheted to a series of important drugs intermediate imidazoles and thiazoles.Application electrospray ionization mass spectrometry captures the key intermediate informations to demonstrate that the reaction mechanism is oxidative addition/reductive elimination pathway.