Catalytic aerobic generation of acyliminium ions through electron-transfer-mediated carbon-carbon bond activation
Catalytic aerobic generation of acyliminium ions through electron-transfer-mediated carbon-carbon bond activation
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DOI：
10.1002/adsc.200303173
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发表时间：
2004-02-01
影响因子：
5.4
通讯作者：
Floreancig, PE
中科院分区：
文献类型：
--
作者：
Aubele, DL;Rech, JC;Floreancig, PE
高苄基酰胺和氨基甲酸酯，在单电子氧化时，经历介晶裂解反应形成酰基异丙基离子。在这些底物上添加亲核基团会导致环化反应形成N-酰基胺。在这些反应中作为光氧化剂的N-甲基喹啉鎓离子在将分子氧引入这些反应中时可以起到催化剂的作用，这代表了一种实现催化需氧氧化的独特方法。在这里，我们提出了一个完整的帐户，我们的研究催化有氧电子转移引发的环化反应的homobenzylic酰胺和氨基甲酸酯，特别强调的作用，酰胺基团，亲核基团，和功能的系链在促进有效的环建设和改变反应机制。
Homobenzylic amides and carbamates, upon single-electron oxidation, undergo mesolytic cleavage reactions to form acyliminium ions. Appending nucleophilic groups to these substrates results in cyclization reactions to form N-acylaminals. The N-methylquinolinium ion that serves as the photooxidant in these reactions can function as a catalyst when dioxygen is introduced into these reactions, representing a unique method for effecting catalytic, aerobic oxidations. Herein we present a full account of our studies on catalytic aerobic electron-transfer-initiated cyclization reactions of homobenzylic amides and carbamates, with particular emphasis on the roles of the amide group, the nucleophilic group, and the functionality in the tether in promoting efficient ring constructions and altering reaction mechanisms.