Electrochemical Synthesis of Allylic Amines from Terminal Alkenes and Secondary Amines.
Electrochemical Synthesis of Allylic Amines from Terminal Alkenes and Secondary Amines.
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DOI：
10.1021/jacs.1c11763
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发表时间：
2021-12
影响因子：
15
通讯作者：
Dian Wang;Karina Targos;Zachary K. Wickens
中科院分区：
文献类型：
--
作者：
Dian Wang;Karina Targos;Zachary K. Wickens
烯丙胺是合成多种生物活性胺产品的有价值的合成靶标。目前的烯丙基C-H胺化策略对于可行的N-取代基来说仍然是有限的。在这里，我们公开了一种通过偶联两个丰富的起始原料：仲胺和未活化的烯烃来制备脂肪族烯丙基胺的新工艺。这种氧化转化是通过在硫代菲和烯烃底物之间电化学生成亲电加合物来进行的。用脂肪胺、亲核试剂和碱处理这些加合物，可以得到高产率的烯丙基胺产品。这一合成策略也适用于原料气态烯烃在1大气压下的官能化。在1-丁烯的情况下，观察到高的Z-选择性巴曲化。然而，这一策略并不局限于合成简单的构建块；复杂的生物活性分子适合作为烯烃和胺偶联伙伴。初步的机理研究表明，乙烯基硫杂菲盐是关键的反应中间体。
Allylic amines are valuable synthetic targets en route to diverse biologically active amine products. Current allylic C-H amination strategies remain limited with respect to the viable N-substituents. Herein, we disclose a new electrochemical process to prepare aliphatic allylic amines by coupling two abundant starting materials: secondary amines and unactivated alkenes. This oxidative transformation proceeds via electrochemical generation of an electrophilic adduct between thianthrene and the alkene substrates. Treatment of these adducts with aliphatic amine nucleophiles and base provides allylic amine products in high yield. This synthetic strategy is also amenable to functionalization of feedstock gaseous alkenes at 1 atm. In the case of 1-butene, high Z-selective crotylation is observed. This strategy, however, is not limited to the synthesis of simple building blocks; complex biologically active molecules are suitable as both alkene and amine coupling partners. Preliminary mechanistic studies implicate vinylthianthrenium salts as key reactive intermediates.