Titanium-promoted Intramolecular Photoenolization/Diels-Alder Reaction to Construct Polycyclic Terpenoids: Formal Synthesis of Mycoleptodiscin A

查看全文 作　　者：Dongsheng [1]Xue;Mengmeng [1]Xu;Chaoying [1]Zheng;Baochao [1]Yang;Min [1]Hou;Haibing [2]He;Shuanhu [1,2]Gao 机构地区：[1]Shanghai Key Laboratory of Green Chemistry and Chemical Processes,School of Chemistry and Molecular Engineering,East China Normal University,3663N Zhongshan Road,Shanghai 200062,China;[2]Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development,East China Normal University,3663N Zhongshan Road,Shanghai 200062,China 出　　处：《Chinese Journal of Chemistry》索引2019年第37卷第2期,共5页 基　　金：the National Basic Research Program of China (973 Program 2015CB856600);the National Natural Science Foundation of China (21772044);the 'National Young Top-Notch Talent Support Program', Program of Sha nghai Academic/Tech no logy Research Leader (18XD1401500), Program of Shanghai Science and Technology Committee (18JC1411303);'the Fundamental Research Funds for the Central Universities' for generous financial support. 摘　　要：Summary of main observation and conclusion A titanium-promoted intramolecular photoenolization/Diels-Alder (PEDA) reaction was developed to construct the core skeleton of aromatic polycyclic terpenoids bearing an all-carbon quaternary center on the benzylic position. Titanium(Ⅳ) isopropoxide [Ti(Oi-Pr)4] plays a key role during the photo cycloaddition, which may help to accelerate the in teraction between dienophile and the stereo-hi ndered diene species as well as control the diastereoselectivity. This photolysis provides a new solution for the stereospecific formation core structures of aromatic abietane diterpenoids and sesquiterpenoids, which have multiple functional groups for the further transformations. As a synthetic application, it was successfully used in the synthesis of indolosesquiterpenoid mycoleptodiscin A. 关 键 词：Titanium-promoted INTRAMOLECULAR Photoenolization CONSTRUCT POLYCYCLIC TERPENOIDS