Dibenzo[b,fi[1,5]diazocines are a class of eight-membered heterocycles,which exhibit unique rigid saddle-shaped structure and possess inherent chirality.In this study,we report a convenient and straightforward method ...Dibenzo[b,fi[1,5]diazocines are a class of eight-membered heterocycles,which exhibit unique rigid saddle-shaped structure and possess inherent chirality.In this study,we report a convenient and straightforward method for the catalytic enantioselective synthesis of these unique chiral molecules through chiral phosphoric acid-catalyzed dimerization of 2-acylbenzoisocyanates.Notably,the addition of corresponding 2-acylaniline as the co-catalyst significantly improved the efficiency of these reactions,and a simple phase separation operation resulted in products with excellent enantiopurity.Experimental studies were performed to elucidate the mechanism behind these reactions,leading to the proposal of a plausible reaction mechanism based on the study findings.展开更多
基金The authors gratefully acknowledge NSFC(grant nos.22222107,22171186)China Postdoctoral Science Foundation(2023M742365)+2 种基金Postdoctoral Fellowship Program of CPSF(GZC20231671)ShanghaiTech University start-up funding for financial support.Prof.Guangxin Liang was acknowledged for sharing the optical rotation polarimeter,and Mr.Huanchao Gu was acknowledged for the assistance with X-ray crystallographic analysissupport from Analytical Instrumentation Center(#SPST-AIC10112914),SPST,ShanghaiTech University.
文摘Dibenzo[b,fi[1,5]diazocines are a class of eight-membered heterocycles,which exhibit unique rigid saddle-shaped structure and possess inherent chirality.In this study,we report a convenient and straightforward method for the catalytic enantioselective synthesis of these unique chiral molecules through chiral phosphoric acid-catalyzed dimerization of 2-acylbenzoisocyanates.Notably,the addition of corresponding 2-acylaniline as the co-catalyst significantly improved the efficiency of these reactions,and a simple phase separation operation resulted in products with excellent enantiopurity.Experimental studies were performed to elucidate the mechanism behind these reactions,leading to the proposal of a plausible reaction mechanism based on the study findings.
