Photoredox-Catalyzed Generation of Tertiary Anions from Primary Amines via a Radical Polar Crossover.
Photoredox-Catalyzed Generation of Tertiary Anions from Primary Amines via a Radical Polar Crossover.
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DOI：
10.1002/anie.202317563
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发表时间：
2024-01
影响因子：
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通讯作者：
Austin D Marchese;Julia R Dorsheimer;T. Rovis
中科院分区：
文献类型：
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作者：
Austin D Marchese;Julia R Dorsheimer;T. Rovis
本文报道了一种由α-叔伯胺通过脱氨基自由基-极性交换生成叔碳负离子的方法。在这种方法中可以使用各种苄型胺和氨基酯，后者参与新的“氮杂-Reformatsky”反应。电子趋势与反应效率的稳定性所产生的负碳离子。这些阴离子可以被不同的亲电试剂捕获，包括醛、酮、亚胺、迈克尔受体和H2O/D2 O。选择性阴离子的形成可以在另一个等价的或更多的酸性C-H键的存在下以分子间和分子内的方式实现。机理研究表明，一个离散的碳负离子中间体的中介作用。
A method for the generation of tertiary carbanions via a deaminative radical-polar crossover is reported using redox active imines from α-tertiary primary amines. A variety of benzylic amines and amino esters can be used in this approach, with the latter engaging in a novel "aza-Reformatsky" reaction. Electronic trends correlate the stability of the resulting carbanion with reaction efficiency. The anions can be trapped with different electrophiles including aldehydes, ketones, imines, Michael acceptors, and H2 O/D2 O. Selective anion formation can be achieved in the presence of another equivalent or more acidic C-H bond in both an inter- and intramolecular fashion. Mechanistic studies suggest the intermediacy of a discrete carbanion intermediate.