Selective Functionalization of Aminoheterocycles by a Pyrylium Salt

Abstract

The functionalization of aminoheterocycles by using a pyrylium tetrafluoroborate reagent (Pyry-BF₄ ) is presented. This reagent efficiently condenses with a great variety of heterocyclic amines and primes the C-N bond for nucleophilic aromatic substitution. More than 60 examples for the formation of C-O, C-N, C-S, or C-SO₂ R bonds are disclosed herein. In contrast to C-N activation through diazotization and polyalkylation, this method is characterized by its mild conditions and impressive functional-group tolerance. In addition to small-molecule derivatization, Pyry-BF₄ allows the introduction of functional groups in a late-stage fashion to furnish highly functionalized structures.

Keywords: C−N activation; amination; heterocycles; late-stage functionalization; pyrylium.