Natural products inspired[3+2]cycloaddition enables efficient construction of hydroxylated tetrahydrofuran acetals and concise syntheses of lignans  

作　　者：Dong-Yue Cai Weiming Shi Zhao-Hui Jin Zhi-Xiang Yu Jin-Xin Zhao Jian-Min Yue 

机构地区：[1]State Key Laboratory of Drug Research,Shanghai Institute of Materia Medica,Chinese Academy of Sciences,Shanghai 201203,China [2]University of Chinese Academy of Sciences,Beijing 100049,China [3]Beijing National Laboratory for Molecular Sciences(BNLMS),Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education,College of Chemistry,Peking University,Beijing 100871,China

出　　处：《Science China Chemistry》2024年第7期2306-2313,共8页中国科学（化学英文版）

基　　金：supported by the Shanghai Pujiang Program(22PJ1415800);the National Natural Science Foundation of China(22237007,T2192972);the Youth Innovation Promotion Association of Chinese Academy of Sciences(2022282);the Laboratory for Molecular Engineering of Chiral Drugs,Shanghai Jiao Tong University(SMECD2022005);the High-Performance Computing Platform of Peking University。

摘　　要：Mimicking biosynthetic pathways of hongkonoids led to the development of a new Cu(Ⅰ)-catalyzed[3+2]cycloaddition ofα-hydroxyketone andβ-keto enol ethers,affording tetrahydrofuran acetals in a highly diastereoselective manner and 100%atom economy.Computational studies on the mechanism disclosed a concerted but asynchronous Michael addition/aldol reaction.Of the same importance,this methodology provides a practical biomimetic approach for one-step construction of the dibenzylbutyrolactol lignan backbone starting from two phenyl propane derivatives,opening up a powerful new approach for lignan synthesis,which is showcased by succinct total syntheses of two biologically important aryltetralin-type lignans,β-apopicropodophyllin and cycloolivil.Given the mild and operationally simple conditions,the developed chemistry might have a promising prospect in potential industrial applications.

关 键 词：[3+2]cycloaddition transition-metal catalysis TETRAHYDROFURAN lignans natural products 

分 类 号：O626[理学—有机化学] O629[理学—化学]