Three‐Component Synthesis of Amine Derivatives Using Benzylic and Allylic Alcohols as N‐Alkylating Agents in the Absence of External Catalysts and Additives

Abstract

AbstractThe direct employment of benzylic and allylic alcohols as N‐alkylating agents provides a useful synthetic route for amine derivatives by avoiding the preactivation of the hydroxy groups of alcohols. Herein we report a novel by‐product‐catalyzed three‐component synthesis of amine derivatives from readily available benzylic and allylic alcohols, acyl chlorides (chloroformates or sulfonyl chlorides), and hexamethyldisilazane (HMDS). In the absence of external catalysts and additives, a range of benzylic and allylic alcohols have been transformed into the corresponding N‐alkyl amides (carbamates or sulfonamides) in good to excellent yields. Furthermore, by‐product TMSCl and its decomposition into HCl have been found to be responsible for promoting the three‐component reaction of benzylic (or allylic) alcohols with acyl chlorides (chloroformates or sulfonyl chlorides) and HMDS.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)