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

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• 作者：Christo S. Sevov ; Jianrong (Steve) Zhou ; John F. Hartwig
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：July 25, 2012
• 年：2012
• 卷：134
• 期：29
• 页码：11960-11963
• 全文大小：303K
• 年卷期：v.134,no.29(July 25, 2012)
• ISSN：1520-5126

文摘

The intermolecular addition of N鈥揌 bonds to unactivated alkenes remains a challenging, but desirable, strategy for the synthesis of N-alkylamines. We report the intermolecular amination of unactivated 伪-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鈥揌 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.