Electrochemical Synthesis of Imino‐C‐Nucleosides by “Reactivity Switching” Methodology for in situ Generated Glycoside Donors
Electrochemical Synthesis of Imino‐C‐Nucleosides by “Reactivity Switching” Methodology for in situ Generated Glycoside Donors
复制标题
通过“反应性转换”方法电化学合成亚氨基-C-核苷，原位生成糖苷供体
DOI：
10.1002/ejoc.202100106
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发表时间：
2021
影响因子：
2.8
通讯作者：
Chiba Kazuhiro
中科院分区：
文献类型：
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作者：
Okamoto Kazuhiro;Tsutsui Mizuki;Morizumi Haruka;Kitano Yoshikazu;Chiba Kazuhiro
通过控制电化学生成的亚胺阳离子的异头反应性，实现了未活化脯氨醇的氧化还原诱导的区域选择性C（sp3）-HC-糖苷化。机理研究表明，中间体以共价氮杂核糖或亚胺阳离子的形式就地汇集，中间体的亲电性可以通过改变共存酸来调节。 我们发现传统糖化学的武装/解除武装类比概念可以适用于我们的C-糖苷化反应。最后，我们发明了一种逻辑合成方法，命名为“反应性转换”概念，并基于此方法合成了一系列亚氨基-C-核苷（C-azanucleoside）。
Redox‐induced regioselective C(sp3)‐HC‐glycosidation for unactivated prolinols was achieved by controlling the anomeric reactivity of electrochemically generated iminium cations. A mechanistic study revealed that the intermediate was pooled as covalent azaribose or iminium cation speciesin situ, and the electrophilicity of intermediates can be adjusted by changing coexisting acids. We found that the armed/disarmed analogy concept of traditional glycochemistry can be adapted to ourC‐glycosidation reaction. Finally, we invented a logical synthetic methodology, named “reactivity switching” concept, and synthesized a series of imino‐C‐nucleosides (C‐azanucleosides) based on this methodology.