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Palladium-catalyzed C–H glycosylation and retro Diels–Alder tandem reaction via structurally modified norbornadienes (smNBDs)
Chemical Science ( IF 7.6 ) Pub Date : 2021-08-31 , DOI: 10.1039/d1sc03569j Yang An 1 , Bo-Sheng Zhang 2 , Ya-Nan Ding 1 , Zhe Zhang 1 , Xue-Ya Gou 1 , Xue-Song Li 1 , Xiaolei Wang 1 , Yuke Li 3 , Yong-Min Liang 1
Chemical Science ( IF 7.6 ) Pub Date : 2021-08-31 , DOI: 10.1039/d1sc03569j Yang An 1 , Bo-Sheng Zhang 2 , Ya-Nan Ding 1 , Zhe Zhang 1 , Xue-Ya Gou 1 , Xue-Song Li 1 , Xiaolei Wang 1 , Yuke Li 3 , Yong-Min Liang 1
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This report describes palladium-catalyzed C–H glycosylation and retro Diels–Alder tandem reaction via structurally modified norbornadienes (smNBDs). smNBDs were proposed to regulate the reactivity of the aryl-norbornadiene-palladacycle (ANP), including its high chemoselectivity and regioselectivity, which were the key to constructing C2 and C3 unsubstituted C4-glycosidic indoles. The scope of this substrate is extensive; the halogenated six-membered and five-membered glycosides were applied to the reaction smoothly, and N-alkyl (primary, secondary and tertiary) C4-glycosidic indoles can also be obtained by this method. In terms of mechanism, the key ANP intermediates characterized by X-ray single-crystal diffraction and further controlled experiments proved that the migration-insertion of smNBDs with phenylpalladium intermediate endows them with high chemo- and regioselectivity. Finally, density functional theory (DFT) calculation further verified the rationality of the mechanism.
中文翻译：
通过结构修饰的降冰片二烯 (smNBD) 进行钯催化的 C-H 糖基化和逆狄尔斯-阿尔德串联反应
本报告描述了钯催化的 C-H 糖基化和通过结构修饰的降冰片二烯 (smNBD) 进行的逆狄尔斯-阿尔德串联反应。smNBDs 被提议用于调节芳基降冰片二烯钯环 (ANP) 的反应性，包括其高化学选择性和区域选择性，这是构建 C2 和 C3 未取代的 C4-糖苷吲哚的关键。这种基材的范围很广；卤代六元和五元糖苷反应顺利，N-烷基（伯、仲和叔）C4-糖苷吲哚也可以通过该方法获得。在机理方面，通过 X 射线单晶衍射表征的关键 ANP 中间体和进一步的受控实验证明，smNBDs 与苯基钯中间体的迁移插入赋予它们高化学和区域选择性。最后，密度泛函理论（DFT）计算进一步验证了该机制的合理性。
更新日期：2021-09-15
中文翻译：
通过结构修饰的降冰片二烯 (smNBD) 进行钯催化的 C-H 糖基化和逆狄尔斯-阿尔德串联反应
本报告描述了钯催化的 C-H 糖基化和通过结构修饰的降冰片二烯 (smNBD) 进行的逆狄尔斯-阿尔德串联反应。smNBDs 被提议用于调节芳基降冰片二烯钯环 (ANP) 的反应性，包括其高化学选择性和区域选择性，这是构建 C2 和 C3 未取代的 C4-糖苷吲哚的关键。这种基材的范围很广；卤代六元和五元糖苷反应顺利，N-烷基（伯、仲和叔）C4-糖苷吲哚也可以通过该方法获得。在机理方面，通过 X 射线单晶衍射表征的关键 ANP 中间体和进一步的受控实验证明，smNBDs 与苯基钯中间体的迁移插入赋予它们高化学和区域选择性。最后，密度泛函理论（DFT）计算进一步验证了该机制的合理性。
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