Nature catalysis: the research group of Professor Shi Zhuangzhi of Nanjing University has made progress in the regulation and control of boronization by copper catalysis

Borate esters are widely used in materials, drugs and chemical synthesis In recent years, the preparation of borate esters by transition metal catalyzed coupling has attracted people's attention, which has the advantages of a wide range of substrates and high functional group compatibility Professor Shi Zhuangzhi, State Key Laboratory of coordination chemistry, School of chemistry and chemical engineering, Nanjing University, has made a series of achievements in the field of selective cutting of boron by inert chemical bonds In 2016, the research group developed nickel catalyzed selective C-N bond activated decarbonylation of aromatic amides (angelw Chem Int ed 2016, 55, 8718) In 2017, the research team used copper catalyst to realize the stereospecific construction of CIS monofluoroolefins (angelw Chem Int ed 2017, 56, 13342) by C-F activation and boration of gemodifluoroolefins This year, the research group also realized the copper catalyzed asymmetric C-F activated boration reaction with trifluoromethylene, and synthesized a series of bifluoroethylene hydrocarbons containing borates with high stereoselectivity (chem 2018.4, 2201) In addition, the research team also realized the c-n-activated boration of fatty amines (angel Chem Int ed 2018, DOI: 10.1002/anie.201809608) Among the borate ester compounds, there is a kind of multiboron compounds containing more than two borate ester groups on the same or adjacent carbon atoms Due to the synergistic effect between boron and boron, it has very special reaction activity and can efficiently construct multiple carbon carbon bonds and carbon heterobonds at the same time It is a kind of very important organic synthons, so it has been widely studied in recent years However, there are few studies on the synthesis of these compounds, especially the tetrasubstituted boron compounds are almost blank Traditional methods often use different raw materials and build different products How to develop a general method, using the same raw materials to synthesize different kinds of boron compounds is an important challenge Recently, Professor Shi Zhuangzhi's research group has realized the C-F bond can be controlled and cut off by using copper catalyst to synthesize 1,2-diboron, 1,1,2-triboron and 1,1,1,2-tetraboron compounds The strategy can selectively convert the same bifluoroethylene to three kinds of boron compounds only by fine-tuning the catalytic system After isotope experiments, using high-resolution, on-line infrared tracking, intermediate capture and other experimental analysis, the research team deduced a very complex but reasonable reaction path This achievement was published online on naturecatalysis (DOI: 10.1038 / s41929-018-0147-9) under the title of "highly tunable multi boundary of gem difluoroalkenes via copperaalysis" Dr Hu Jiefeng (now associate professor of Nanjing University of Technology) of School of chemistry and chemical engineering of Nanjing University is the first author of this paper, and Mr Zhao Yue, National Key Laboratory Responsible for crystal analysis The above research work has been funded by the "youth thousand" program of the Central Organization Department, the National Natural Science Foundation, the "entrepreneurship and Innovation Program" of Jiangsu Province, and the State Key Laboratory of coordination chemistry.