Ag(i)-Promoted homo-dimerization of 2-(alk-2-yn-1-onyl)-1-alkynylbenzenes via a [4 + 2] cycloaddition of benzopyrylium ions: access to structurally unique naphthalenes

Abstract

Herein we report a Ag(I)-promoted homo-dimerization of 2-(alk-2-yn-1-onyl)-1-alkynylbenzenes for the synthesis of structurally novel and functionalized naphthalene derivatives. This transformation exhibits a broad scope for the alkyl as well as aryl groups present on alkynes. Observations made from control experiments suggest the possible mechanism as (i) the homo-dimerization of the in situ generated benzopyrylium ion intermediates through a head-tail [4 + 2] cycloaddition, followed by (ii) the competitive ring-opening vs. decarbonylative aromatization of the adduct to give formylated and deformylated naphthalenes, respectively.