Research group of Mei Tiansheng, Shanghai Institute of organic chemistry: new progress in electrooxidation promoted functionalization of hydrocarbon bonds

In the past decade, the transition metal catalyzed selective hydrocarbon bond functionalization has become an effective tool for the construction of C-C and c-y bonds However, the disadvantage of these reaction systems is the need for equivalent chemical oxidants It is easy to produce by-products, poor atomic economy or expensive to use equivalent oxidants Therefore, the development of new oxidation systems is one of the challenges in the field of transition metal catalyzed hydrocarbon bond functionalization Electrochemical oxidation is an environmentally friendly solution that requires the use of conventional methods of equivalent chemical oxidants In recent years, the research group of Mei Tiansheng, researcher of Shanghai Institute of organic chemistry, has developed a series of palladium catalyzed electrochemical promoted hydrocarbon bond functionalization reactions, which have realized selective oxidation of alkanes, acylation and alkylation of aromatics (j.am.chem.soc 2017, 139, 3293; org Lett 2017, 19, 2905; chem Commun 2017, 53, 12189; ACS catalyst 2018, 8, 7179) (Figure 1) Although great progress has been made in this field, the use of metal mechanochemical hydrocarbon bond functionalization is mainly limited to the use of precious metal catalysts and the need to use electrolytic cells with membranes Figure 1 Palladium catalyzed electro oxidation promoted hydrocarbon bond functionalization Recently, Mei Tiansheng group realized the first copper catalyzed electro oxidation promoted aromatics hydrocarbon bond amination The reaction was carried out at room temperature and did not require the use of an electrolytic cell with a membrane (j.am.chem.soc 2018, DOI: 10.1021/jacs.8b07380) This reaction provides an efficient, economic and environmentally friendly way for the synthesis of aniline Using n-bu4ni as redox medium is very important for the transformation The kinetic, isotopic effect, cyclic voltammetry and free radical inhibition experiments were systematically studied The results showed that the reaction was realized by single electron transfer (set), and the high valence Cu (III) species also participated in the reaction This study provides a more efficient way for transition metal catalyzed electrochemical functionalization of hydrocarbon bonds Figure 2 The above research of copper catalyzed electrooxidation promoted hydrocarbon bond amination was supported by the youth thousand talents program of the Central Organization Department, the National Natural Science Foundation of China, Shanghai Municipal Science and Technology Commission, Chinese Academy of Sciences, Shanghai Institute of organic chemistry of Chinese Academy of Sciences and the State Key Laboratory of organometallic chemistry.