Amine-directed Mizoroki–Heck arylation of free allylamines

Abstract

The transition metal-catalyzed Mizoroki–Heck reaction is a powerful method to synthesize C–C bonds, allowing access to several important pharmaceuticals. Traditionally free amines have not been compatible with these approaches due to oxidation of the amine by the transition metal or other side reactions. However, the functionalization of unprotected allylamines is particularly attractive due to their prevalence in various biologically active molecules. Herein we report the palladium-catalyzed selective monoarylation of free allylamines using aryl iodides. The strategy works on primary, secondary, and tertiary amines, making it very general. Our monoarylation method is scalable and works on aryl iodides with a variety of substituted arene or heterocycle motifs, including chromophoric substrates.