Study Of Tertiary Amine Formation By Hydrogen-borrowing And Acylamine Fomation By Photocatalysis

In recent years, the research and exploration of simple, cheap, readily available, mild and environmentally benign synthetic methods have attracted continuous interest since the concept "green chemistry" and "atom economy" were put forward. The construction of C-N bond is becoming focus of study and considerable progress has been achieved, many efficient methods for the formation of secondary amine, tertiary amine and amide have been realized. However, direct animation of nitro compounds with alcohols has not been reported. Herein, we report a highly selective ruthenium-catalyzed C-N bond formation method based on the common and cheap alcohols and nitro compounds. The first step in this reaction is the dehydrogenation of alcohol to its corresponding aldehyde with the release of two hydrogen using Ru(CO)(H)2(PPh3)3/IPr·HCl as the catalyst, The nitro group then was reduced to amine which will form the corresponding imine intermediate then was reduced to secondly amine with the hydrogen released by the alcohol oxidation step, and subsequently the reaction follows the same route as alkylation of amine. Ultimately, the alcohol oxidation, nitro reduction, imine reduction and C-N bond formation were realized in a cascade and in one pot, providing a new greener synthetic method for the preparation of nitrogen-containing organic compounds.Light energy is a safe, green, renewable energy source and is environmentally benign. When treated tertiary amine with light, the tertiary amine was transferred to amide, in the absence of transition-metal catalyst at room temperature. Solvents play a important role in this transformation. The reaction conditions has been optimized. However, the substrate scope is not completed due to the time limitation.In conclusion, we developed a tertiary amine formation procedure from nitro arenes and alcohols using the borrowing hydrogen strategy. Under light, the tertiary amines can be transformed to amides in the absence of transition-metal at room temperature.