An Approach to Functionally Embellished o-Alkynylbenzoates or Furan-3(2H)-ones from Diynones and DMAD: Controlled Divergence and Product Selectivity

Abstract

The discovery of reaction regime controlled product diversification in a one-pot reaction between diynones and dimethyl-1,3-acetonedicarboxylate (DMAD) to selectively furnish either functionally unique pentasubstituted o-alkynylbenzoates or fully substituted furan-3(2H)-ones is delineated. The potential of these two versatile platforms to enter new utilitarian chemical space has also been explored.

Multicomponent and Metal‐Free Diels–Alder/Aromatization Approach to the Stereospecific Synthesis of E‐(Hetero)Stilbenes and Diarylacetylenes

“…Over the years, new methods of accessing this class of compounds were developed, such as addition‐elimination strategies to aromatic carbonyl compounds, [52,53] nucleophilic aromatic substitution on electron poor arenes [54,55] or photochemical alkynylation of electron rich arenes [56] . Moreover, an anionic cascade between dimethyl‐1,3‐acetonedicarboxylate and diynones to furnish ortho ‐alkynylbenzoates has been recently reported [57] . This class of compounds is highly attractive for pharmaceutical and material science applications due to the high conjugation and structural rigidity [58] .…”

“…[56] Moreover, an anionic cascade between dimethyl-1,3acetonedicarboxylate and diynones to furnish ortho-alkynylbenzoates has been recently reported. [57] This class of compounds is highly attractive for pharmaceutical and material science applications due to the high conjugation and structural rigidity. [58] Thus, the synthesis of diarylacetylenes by our synthetic protocol could then offer a novel and metal-free access to this strategic class of compounds.…”