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

作　　者：Dongsheng Xue Mengmeng Xu Chaoying Zheng Baochao Yang Min Hou Haibing He Shuanhu 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》2019年第2期135-139,共5页中国化学（英文版）

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 

分 类 号：O6[理学—化学]