Yu Shouyun and Zhu Chengjian, professors of Nanjing University, systematically summarized the research progress of the enantioselective reaction of nickel, palladium, copper and chromium transition metals with the synergistic catalysis of photo oxidation-reduction, and discussed the reaction mechanism in detail.
Visible light redox catalysis can produce high active intermediates such as free radicals or free radical ions under mild conditions, which has great potential in organic synthesis. Photocatalytic oxidation-reduction reaction is strongly dependent on the catalytic performance of photocatalyst. The excited Photocatalyst (or photosensitizer) can activate the reaction substrate by means of electron transfer, energy transfer or atom transfer. Because photocatalyst is not directly involved in the formation or fracture of chemical bond, the range of reaction substrate which can be activated by this reaction mode is limited. Moreover, due to the high activity of free radical species, it is difficult to realize the enantioselective photocatalytic redox system. In order to further expand the application scope of photocatalytic oxidation-reduction reaction, the transition metal and photocatalytic reaction mode has been concerned. In this reaction mode, the photocatalyst can transfer energy or electron with the transition metal, and the transition metal participates in the formation or fracture of chemical bond; the oxidation-reduction ability of photocatalyst is used to change the valence state of the transition metal catalyst so that it has the catalytic activity that the traditional transition metal catalyst does not have. This mode has greatly expanded the scope of application of photocatalysis, and the enantioselective reaction can also be realized by introducing a suitable transition metal chiral ligand (as shown in the figure).
In recent years, remarkable progress has been made in the field of enantioselective photo oxidation reduction and transition metal co catalysis. Recently, Professor Yu Shouyun and Professor Zhu Chengjian of Nanjing University wrote a review of enabling dual transition metal / photoedox for SCI. China chem Catalysis "systematically summarizes the research progress in this field, introduces the enantioselective reactions of transition metals of nickel, palladium, copper and chromium with the synergistic catalysis of photoreduction, and discusses the reaction mechanism in detail.
The author also points out four problems worthy of further study in this field
(1) Rich synergetic catalysis system. At present, only four metals (nickel, palladium, copper and chromium) can cooperate with photo oxidation-reduction to realize enantioselective reaction. It is an urgent task to further expand the transition metal asymmetric catalytic system matching photo oxidation-reduction. (2) The type of photo oxidation-reduction and transition metal co catalysis was expanded. The successful reactions mainly focus on cross coupling reactions, and other reaction types also need to be developed. （3） A single transition metal bifunctional catalytic system was developed. Two kinds of catalysts are usually needed for a successful system: photocatalyst and transition metal catalyst. Some transition metals also have photocatalytic activity, so the development of new bifunctional chiral catalysts, which can be used as both redox and asymmetric transition metal catalysts, is also worthy of attention. (4) The reaction mechanism was studied. At present, the research on the reaction mechanism is not deep enough. A thorough understanding of the reaction mechanism is conducive to the development of new catalytic systems and reactions. For details, see: Hong Hao Zhang, Hui Chen, Chen Zhu *, Shouyun Yu *. A review of enabling dual transition metal / photoedox catalysis. SCI. China chem., https://doi.org/10.1007/s11426-019-9701-5. This article will be included in the "special journal of celebrating the 100th anniversary of the founding of the Chemistry Department of Nanjing University", please pay attention.
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About the author
Professor Yu Shouyun graduated from the school of chemistry and chemical engineering of Nanjing University in 2001 with a bachelor's degree. In the same year, he entered Shanghai Institute of organic chemistry, Chinese Academy of Sciences to study for a Ph.D. under the guidance of researcher Ma Dawei. In 2006, he obtained his Ph.D. degree and stayed as an assistant researcher. From 2007 to 2010, he conducted postdoctoral research in Jeffrey bode's group at the University of Pennsylvania. In September 2010, he was employed as an associate professor and project leader of the school of chemistry and chemical engineering of Nanjing University, and was promoted to a professor in 2016. The research focuses on the target oriented methodology of organic synthesis (free radical chemistry and Organic Photochemistry), the total synthesis of natural products with physiological activity and their chemical biology. He has won Thieme Chemistry Journals Award (2012), the second prize of National Natural Science Award (2007, the fourth adult).
Professor Zhu Chengjian received his Ph.D. from Shanghai Institute of organic science, Chinese Academy of Sciences in 1996, and then went to University de Bourgogne in France, University of Oklahoma and University of Houston in the United States to engage in post doctoral research. He was employed as an associate professor of Nanjing University in 2000 and a professor in 2003. In 2006, he was selected into the "new century talent support plan" of the Ministry of education, and in 2014, he won the Baosteel outstanding teacher award. Member of the Organic Chemistry Committee of the Chinese chemical society, and editorial board member of organic chemistry and molecular.
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