Iridium-Catalyzed Intermolecular Hydroamination of Unactivated Aliphatic Alkenes with Amides and Sulfonamides

The intermolecular addition of N–H bonds to unactivated
alkenes remains a challenging, but desirable, strategy for the synthesis
of N-alkylamines. We report the intermolecular amination
of unactivated α-olefins and bicycloalkenes with arylamides
and sulfonamides to generate synthetically useful protected amine
products in high yield. Mechanistic studies on this rare catalytic
reaction revealed a resting state that is the product of N–H
bond oxidative addition and coordination of the amide. Rapid, reversible
dissociation of the amide precedes reaction with the alkene, but an
intramolecular, kinetically significant rearrangement of the species
occurs before this reaction with alkene.

将N–H键分子间加成至未活化烯烃，仍是一条兼具挑战性与应用价值的N-烷基胺合成策略。本文报道了未活化α-烯烃与双环烯烃分别与芳基酰胺、磺酰胺发生的分子间胺化反应，可高产率获得合成应用价值优异的保护型胺类产物。针对这一罕见催化反应的机理研究显示，其静息态为N–H键氧化加成并结合酰胺后生成的中间体。在与烯烃发生反应前，酰胺会经历快速且可逆的解离；而在该烯烃加成反应发生之前，该物种还会完成一次动力学上具有显著影响的分子内重排过程。