Construction of alkyl-substituted 7-norbornenones through Diels-Alder cycloaddition of electron-deficient olefins and a cyclopentadienone derivative generated in situ  

作　　者：Shanxiang Liu Jinxin Wang Yuyong Ma Xin Cao Wei-Dong Zhang Ang Li 

机构地区：[1]School of Traditional Chinese Pharmacy,China Pharmaceutical University,Nanjing 211198,China [2]State Key Laboratory of Bioorganic and Natural Products Chemistry,Center for Excellence in Molecular Synthesis,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,University of Chinese Academy of Sciences,Shanghai 200032,China [3]State Key Laboratory of Innovative Natural Medicine and Traditional Chinese Medicine Injections,Jiangxi Qingfeng Pharmaceutical Co.Ltd.,Ganzhou 341000,China [4]Department of Phytochemistry,School of Pharmacy,Second Military Medical University,Shanghai 200433,China

出　　处：《Chinese Chemical Letters》2022年第4期2041-2043,共3页中国化学快报（英文版）

基　　金：supported by Ministry of Science and Technology (National Key Research and Development Program of China,Nos. 2019YFC1711000 and 2018YFA0901900);National Natural Science Foundation of China (Nos. 21931014, 21525209, 21621002,21772225, 21761142003 and 82003624);Chinese Academy of Sciences (Strategic Priority Research Program, No. XDB20000000;International Partner Program, No. 121731KYSB20190039;Key Research Program of Frontier Sciences, No. QYZDB-SSW-SLH040);Science and Technology Commission of Shanghai Municipality (Nos.17XD1404600 and 20YF1458700);State Key Laboratory of Innovative Natural Medicine and Traditional Chinese Medicine Injections(No. QFSKL2017002);K.C. Wong Education Foundation。

摘　　要：Dimeric sesquiterpenoids possessing densely substituted 7-norbornenone/7-norbornenol motifs pose a considerable challenge for chemical synthesis. From a strategic perspective, one could envision intermolecular Diels-Alder cycloaddition as a straightforward method for assembling alkyl-substituted 7-norbornenones. However, this approach is hindered by lability of the required dienes, namely alkylsubstituted cyclopentadienones. Here we report a one-pot protocol for construction of alkyl-substituted7-norbornenones from electron-deficient olefins and a cyclopentenone derivative. DDQ was found to be an effective oxidant for generating a cyclopentadienone intermediate in situ from the enone. A series of sterically congested 7-norbornenone-containing polycyclic compounds were prepared by using this protocol.

关 键 词：7-Norbornenone Alkyl-substituted cyclopentadienone Diels-Alder cycloaddition Dimeric sesquiterpenoid 

分 类 号：O623.52[理学—有机化学]