Transition-Metal-Free alpha-Arylation of beta-Keto Amides via an Interrupted Insertion Reaction of Arynes

Abstract : Direct alpha-arylation reactions of secondary beta-keto amides with arynes, generated by fluoride-induced elimination of ortho-silyl aryltriflates, are described. The transformation proceeds via an interrupted insertion reaction of arynes and leads to densely functionalized aromatic compounds exhibiting a chiral 'all carbon' quaternary center under transition-metal-free conditions. An organocatalytic asymmetric version of the reaction also proved possible, affording the proof of concept that arynes can be involved in enantioselective transformations.