En Route to Diastereopure Polycyclic γ-Lactones by Iridium-Catalyzed Hydride Transfer  

作　　者：Yang Chen Jingyu Zhang Yecheng Wang Hongguang Du Jiaxi Xu Zhanhui Yang 

机构地区：[1]Department of Organic Chemistry,College of Chemistry,Beijing University of Chemical Technology,Beijing 100029,China

出　　处：《Chinese Journal of Chemistry》2024年第23期3047-3055,共9页中国化学(英文版)

基　　金：supported by the National Key Research and Development Program of China(No.2022YFF0709803);Natural Science Foundation of Beijing Municipality(No.2202041);the High Performance Computing Platform of Beijing University of Chemical Technology(BUCT).

摘　　要：The reductive lactonization strategy provides an efficient access to diastereoenriched polycyclicγ-lactones.However,it is still a formidable challenge to develop an efficient and versatile protocol with excellent levels of diastereocontrol.Herein,we provide a highly diastereoselective and efficient route to diastereopure bi-and polycyclicγ-lactones,by means of an iridium-catalyzed hydride transfer strategy.This method features high levels of diastereocontrol,broad substrate scope,and high catalyst efficiency(S/C=up to 5000).Mechanistic studies suggest that the iridium hydride formation might be the rate-determining step,and that the hydride transfer step be the diastereo-determining step.The large steric hindrance of the iridium hydride species and intramolecular hydrogen bonding are critically key to the diastereocontrol of the hydride transfer process.From the perspectives of configurational analysis and Duniz angles of attack,the nature of diastereocontrol is well rationalized.A more general empirical rule based on facial selectivity analysis for explaining and predicting the stereochemistry is also proposed.

关 键 词：Iridium catalysis Hydride transfer Reductive lactonization Diastereoselectivity control Polycyclic y-lactones Methodology and reactions Sterichindrance Reduction 

分 类 号：TQ225.24[化学工程—有机化工]