Metal-Free [2 + 2 + 2] Cycloaddition of Ynamides with Nitriles to Construct 2,4-Diaminopyridines

Malononitrile dimer as a precursor reactant has been extensively applied in the diversity-oriented synthesis of various heterocyclic motifs, bis-heterocyclic compounds, fused heterocycle derivatives, bicyclic bridged heterocyclic scaffolds, and highly substituted carbocyclic compounds. These remarkable products were synthesized via various types of reactions, such as cycloaddition, cyclocondensation, cascade/domino/tandem reactions along with multi-component reactions. In addition, the flexibility and high reactivity of malononitrile dimer as a multi-functional reagent and its potential to the preparation of novel beneficial scaffolds as well as biologically active molecules signify it as a suitable building block in total synthesis, medicinal chemistry, and dyes. In the present review, the advances in the chemistry of malononitrile dimer as a potent reagent in organic synthesis have been reported in the past to now.

Malononitrile dimer as a privileged reactant in design and skeletal diverse synthesis of heterocyclic motifs

Ten years of progress in the synthesis of six-membered N-heterocycles from alkynes and nitrogen sources

In this work, we provide the first generalized and critical analysis of data on the chemistry of malononitrile dimer (2-aminopropene-1,1,3-tricarbonitrile) – a multifunctional reagent that is widely used for the preparation of diverse heterocyclic systems. The majority of references are from the last 20–25 years.

Heterocyclization reactions using malononitrile dimer (2-aminopropene-1,1,3-tricarbonitrile)

Clean synthesis of novel spiro[indene-2,2’-[1,3,5]-oxathiazine]-1,3-diones in water

Sulfonyl-ketenimine intermediates, generated by the addition of Cu acetylides to sulfonyl azides, are trapped by KSeCN to afford N-sulfonyl-2-alkaneimidoyl selenocyanates in moderate-to-good yields.

Sulfonyl Ketenimines as Key Intermediates in One-Pot Synthesis of N-Sulfonyl-2-alkaneimidoyl Selenocyanates

Fully substituted pyridines were synthesized in moderate to good yields in a one-pot process by the copper-catalyzed sequential reaction of sulfonyl azides with terminal alkynes and 2-aminoprop-1-ene-1,1,3-tricarbonitrile at room temperature.

Copper-Catalyzed Tandem Synthesis of Pentasubstituted Pyridines from Sulfonoketenimides and 2-Aminoprop-1-ene-1,1,3-tricarbonitrile

Regioselective synthesis of pentasubstituted pyridines has been developed in moderate-to-good yields by the reaction of sulfonyl azides, alkynes, and a dialkyl acetylenedicarboxylatetetramethylguanidine adduct catalyzed by CuI in MeCN at room temperature.

Azam Sheikhi

Papers

Sulfonyl Ketenimines as Key Intermediates in One-Pot Synthesis of N-Sulfonyl-2-alkaneimidoyl Selenocyanates

Copper-Catalyzed Tandem Synthesis of Pentasubstituted Pyridines from Sulfonoketenimides and 2-Aminoprop-1-ene-1,1,3-tricarbonitrile

Copper‐Catalyzed Synthesis of Pentasubstituted Pyridines from N‐Sulfonyl Ketenimines, 1,1,3,3‐Tetramethylguanidine, and Acetylene Dicarboxylates

Synthesis of Functionalized N-Sulfonylamidines from N-Sulfonylketenimines and 2-Aminobenzimidazole

Copper‐Catalyzed Synthesis of Pentasubstituted Pyridines from N‐Sulfonyl Ketenimines, 1,1,3,3‐Tetramethylguanidine, and Acetylene Dicarboxylates.