Utility of Acetylenedicarboxylate in Organic Synthesis

Abstract

Although, recent reviews demonstrated intensively on the reactivity of dimethyl acetylenedicarboxylate (DMAD) in organic synthesis, its reactions have still get importance addition in that field. Moreover, and due to the huge amount of published literatures dealing with the reactions of DMAD, we are trying to give more focus on the important missed reactions in addition to give more light to updated publications. DMAD is an organic compound with the formula (C6H6O4), and it is a diester in which the ester groups are conjugated with a triple bond. As such, DMAD is highly electrophilic and a widely employed as a dienophile in cycloaddition reactions, like the Diels–Alder reaction. Many organic compounds specially the heterocyclic ones were prepared via its reactions.

Extremely Rapid Polythioether Synthesis in the Presence of TBD

“…It is well known that the reactivity of dialkyl acetylenedicarboxylate is due to the triple bond connected to two carbonyl groups that makes it very electron-deficient and thus suitable for Michael addition reactions. , Therefore, polymer chemists have adapted this valuable reagent to the macromolecular level and utilized for the synthesis of a wide variety of polymer architectures ranging from linear to nonlinear polymers (hyperbranched and dendrimers). − Taking the benefits of this structure, our group, more recently, has prepared a polyester with electron-deficient triple bonds in the main chain through a condensation reaction of acetylenedicarboxylic acid and 1,4-butanediol . During the postfunctionalization study via thiol–Michael reactions, we detected a double functionalization on the polyester backbone when an organocatalyst such as DBU, TBD, or TMG was used as catalyst.…”

New frontiers in the transition-metal-free synthesis of heterocycles from alkynoates: an overview and current status

“…The robust use of these methods in the synthesis of natural products, pharmaceuticals and bioactive drug candidates has also been discussed. Selected examples of heterocycles accessed by using DMAD and DEAD as coupling units have been reviewed previously; [86][87][88][89][90][91][92] thus they have not been discussed exhaustively here and are excluded from the scope of this review except a few representative examples demonstrating the diversity of transformations.…”

Synthesis and some reactions of 5-carbmethoxymethylidene-4-oxo-1,3-thiazol-2-ylguanidine

“…In addition, imethylacetylene dicarboxylate is widely used in organic synthesis for the construction of five-, six-, and seven-membered heterocyclic systems. [22][23] Substituted 1,3-thiazinones 1 or 1,3-thiazolones 2 are formed in reactions of 1,3-S,N-binucleophiles with substituted thioacetamides, thioureas, 2mercapto(benzo)imidazole, 2-mercapto-1,2,4-triazole, etc., along with DMAD (Scheme 1). In most cases, the formation of 1,3-thiazole cycle occurs.…”

“…In this case, sulfur is attached to an activated multiple bond, and nitrogen attacks the ester group. [22][23][24][25] At the same time, in the case of unsubstituted thiourea and Nalkylthiourea, a six-membered ring is formed. 27 The reactions of various 1,3-N,N-binucleophiles, including those with DMAD, lead to the formation of substituted pyrimidinones 3 or imidazolones 4 (Scheme 1).…”