Electrochemical Synthesis of Allylic Amines from Terminal Alkenes and Secondary Amines
作者:Diana J. Wang、Karina Targos、Zachary K. Wickens
DOI:10.1021/jacs.1c11763
日期:2021.12.29
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
烯丙基胺是合成各种具有生物活性的胺产品的重要合成目标。目前的烯丙基 C-H 胺化策略在可行的N取代基方面仍然有限。在此,我们公开了一种新的电化学方法,通过偶联两种丰富的起始材料:仲胺和未活化的烯烃来制备脂肪族烯丙胺。这种氧化转化通过在噻蒽和烯烃底物之间电化学产生亲电加合物而进行。用脂肪胺亲核试剂和碱处理这些加合物以高产率提供烯丙基胺产物。这种合成策略也适用于原料气态烯烃在 1 个大气压下的官能化。在 1-丁烯的情况下,高Z观察到选择性巴豆酰化。然而,这种策略并不局限于简单构建块的合成;复杂的生物活性分子既适合作为烯烃偶联配偶体,也适合作为胺偶联配偶体。初步的机理研究表明乙烯基蒽盐是关键的反应中间体。