Wallach Daniel R, Stege Patrick C, Shah Jigisha P, Chisholm John D
Department of Chemistry, 1-014 Center for Science and Technology, Syracuse University , Syracuse, New York 13244, United States.
J Org Chem. 2015 Feb 6;80(3):1993-2000. doi: 10.1021/jo5027222. Epub 2015 Jan 16.
Trichloroacetimidates are useful alkylating agents for aromatic amines, requiring only a catalytic amount of a Brønsted acid to facilitate the reaction. Monoalkylation predominates under these conditions. Electron-poor anilines provide superior yields, with electron-rich anilines sometimes showing competitive Friedel-Crafts alkylation. A single flask protocol with formation of the imidate in situ is demonstrated, providing a convenient method for the direct substitution of alcohols with anilines. Reaction with a chiral imidate favors a mechanism that proceeds through a carbocation intermediate.
三氯乙亚胺酯是用于芳香胺的有用烷基化剂，仅需催化量的布朗斯特酸即可促进反应。在这些条件下，单烷基化占主导。缺电子的苯胺能提供更高的产率，富电子的苯胺有时会发生竞争性的傅克烷基化反应。展示了一种在原位形成亚胺酯的单瓶操作方法，为醇与苯胺的直接取代提供了一种便捷方法。与手性亚胺酯反应有利于通过碳正离子中间体进行的反应机理。
