Rhodium-catalyzed Aromatic Electrophilic Amidation And Metal-free Oxidative Decarbonylative Coupling Of Aldehydes With(Aza)arenes

Due to the C-H bond exists extensively in nature. C-H bond activation which needs not prefunctionalization of the C-H bond, shorts the synthetic step, shares the following advantages such as atom economy and step economy is widely used in the formation of C-X(X=C, N, P, S, et. al.) bonds. As C-N and C-C bonds are the most common bond in organic compounds, It is of great significance to develop the C-N and C-C bond via C-H activation.This dissertation consisted of two parts. The first one is focused on rhodium-catalyzed C-H bond activation and electrophilic amidation. The second is focused on the metal-free decarbonylative cross-coupling reactions.Based on the reviews of the Rh-catalyzed C-H bond functionalization in recent years, the development of Rh-catalyzed C-H bond activation and amidation reaction was founded. We have developed an electrophilic amidation via a cationic rhodium(III)-catalyzed(sp2)-H activation with the commercially available N-fluorobenzenesulfonimide as the amino source under external oxidant-free conditions. This amidation requires only a catalytic amount of base and exhibits excellent functional group tolerance and regioselectivity, providing a new avenue in direct(sp2)-H amidation.In part two decarbonylative C-C bond forming reactions in recent years were simply reviewed. A metal-free oxidative decarbonylative coupling of aromatic aldehydes with electron-rich or electron-deficient arenes to produce biaryl compounds was developed. This novel coupling was proposed to proceed via a non-chain radical homolytic aromatic substitution(HAS) type mechanism, based on the substrates scope, ortho-regioselectivity, radical trapping experiments and DFT calculation studies.Then, this metal-free oxidative decarbonylative coupling was applied to the reaction between aliphatic aldehydes with heterocycles under the similar conditions to afford the alkylated products. No alkyl chain rearrangement products were detected.