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-A...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.展开更多
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)+5 种基金Chinese Academy of Sciences (Strategic Priority Research Program, No. XDB20000000International Partner Program, No. 121731KYSB20190039Key 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。
文摘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.
