Palladium- and Nickel-Catalyzed Amination of Aryl Fluorosulfonates

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• 作者：Patrick S. Hanley ; Thomas P. Clark ; Arkady L. Krasovskiy ; Matthias S. Ober ; John P. O’Brien ; Tina S. Staton
• 刊名：ACS Catalysis
• 出版年：2016
• 出版时间：June 3, 2016
• 年：2016
• 卷：6
• 期：6
• 页码：3515-3519
• 全文大小：361K
• 年卷期：0
• ISSN：2155-5435

文摘

Examples of the palladium- and nickel-catalyzed amination of aryl fluorosulfonates with aromatic and alkyl amines are described. Aniline is coupled to a diverse series of aryl fluorosulfonates catalyzed by the combination of CpPd(cinammyl) and Xantphos, and the relative reactivity of aryl fluorosulfonates to undergo Pd-catalyzed amination was compared with other common aryl electrophiles. In addition, we report the direct amination of a phenol by in situ formation of an aryl fluorosulfonate by reaction with sulfuryl fluoride and base followed by subsequent amination to form a new C–N bond. Finally, we report examples of the nickel-catalyzed amination of aryl fluorosulfonates catalyzed by the combination of Ni(COD)₂ and DPPF in the presence of MeCN. The high reactivity of the aryl fluorosulfonate electrophile with generic palladium and nickel catalyst systems, combined with its simple preparation from sulfuryl fluoride will enable commercial amination reactions of abundant phenolic raw materials.