Professor Zhu shoufei and academician Zhou Qilin of Nankai University: rhodium catalyzed B-H bond insertion reaction

As a very important metalloid organic reagent, organoboron compounds are widely used in synthesis Their unique physical and chemical properties make them have a good application prospect in material science and medicine Therefore, the synthesis of organoboron compounds has been widely concerned Some C-B bonding reactions have been developed, but these reactions have their own limitations The structure diversity of the synthesized organoboron compounds is poor, and the synthesis efficiency of some important organoboron compounds is low In 2013, Professor Zhu shoufei and academician Zhou Qilin of Nankai University reported a transition metal catalyzed insertion reaction of carbene into the B-H bond of amine borane adduct and phosphine borane adduct This reaction combines the metal carbene chemistry with the organic boron chemistry It has the characteristics of good functional group tolerance, mild reaction conditions and controllable selectivity It provides a new method for the synthesis of organic boron compounds Subsequently, other research groups have successfully applied a variety of new catalysts to the reaction, and further expanded the range of substrates However, up to now, carbene precursors used in B-H bond insertion reactions are all stable diazo compounds containing α - electron absorbing groups (such as ester group, ketone carbonyl group, trifluoromethyl group, etc.), which results in the structural limitations of B-H bond insertion products and affects their subsequent synthesis and transformation Recently, academician Zhou Qilin and Professor Zhu shoufei's team have made important progress in the metal catalyzed insertion reaction of carbene to B-H bond Using Bamford Stevens reaction, the team heated sulfonylhydrazone derived from aldehydes and ketones under alkaline conditions to generate unstable diazo compounds in the field, and realized B-H bond insertion reaction under the catalysis of rhodium complex, and achieved high enantioselectivity using chiral rhodium complex catalyst The new reaction realizes the direct conversion of carbonyl functional groups (aldehydes and ketones) to boron functional groups, and has the characteristics of wide application range of substrates, good tolerance of functional groups and controllable selectivity Due to the rich types of carbonyl compounds, this reaction laid a foundation for the synthesis of organoboron compounds with various structures Because of the absence of α - electron absorption group, the products can be converted into many functional groups, and the enantioselectivity is well maintained in the conversion process This achievement was recently published in J am Chem SOC (J am Chem SOC 2018, 140, 10663) The first author of this paper is master's degree candidate of Nankai University The research was supported by the Foundation Committee, the Ministry of education and Nankai University.