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 diastereoselect...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.展开更多
基金supported by the Shanghai Pujiang Program(22PJ1415800)the National Natural Science Foundation of China(22237007,T2192972)+2 种基金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。
文摘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.
