Studies Of Transition-Metal-Catalyzed Decarboxylative Coupling Reaction Of α,β-unsaturated Carboxylic Acids

In recent years, decarboxylative functionalization has been developed significantly, since it opens a new avenue for the formation of carbon-carbon and carbon-heteroatom bonds. This method has advantages over the conventional transition metal catalyzed cross-coupling reactions concerning not require substrate preactivation process and easy availability and low toxicity of carboxylic acids and high regioselectivity as well as atom and step economy and environmental issues.This paper studied for the methods of decarboxylative cross-coupling reation, and result in the formation of various C-C, C-N bonds to get target productFirst, we studied Cu(NO3)2-catalyzed decarboxylation of α,β-unsaturated carboxylic acids for the preparation of β-nitro styrenes. In this protocol, Cu(NO3)2 was used as both nitrating agent and catalyst, successfully achieve a example of nitrodecarboxylation of α,β-unsaturated acids under mild and additive-free conditions. The protocol is simple, highly regioselective and efficient. Gram-scale applications for the present method were also efficient, it has good prospect for industrialization.Second, We developed a method of nitrile synthesizd via FeCl3-catalysed decarboxylative C-C bond coupling. This protocol use AIBN as substrate, is no need of harsh reaction conditions, is simple and easy to get, safe and green, with good functional group tolerance, electron-withdrawing and electron-rich α,β-unsaturated carboxylic acids all can get the corresponding product.Besides, we have made a research on the mechanism of the reaction, and the possible reaction mechanism was proposed.