Functionalized 2,3'-Bipyrroles and Pyrrolo[1,2-c]imidazoles from Acylethynylpyrroles and Tosylmethylisocyanide.

An efficient method for the synthesis of pharmaceutically prospective but still rare functionalized 2,3'-bipyrroles (in up to 80% yield) by the cycloaddition of easily available acylethynylpyrroles with tosylmethylisocyanide (TosMIC) has been developed. The reaction proceeds under reflux (1 h) in the KOH/THF system. In the t-BuONa/THF system, TosMIC acts in two directions: along with 2,3'-bipyrroles, the unexpected formation of pyrrolo[1,2-c]imidazoles is also observed (products ratio~1:1).

Substituent-Dependent Divergent Synthesis of 2-(3-Amino-2,4-dicyanophenyl)pyrroles, Pyrrolyldienols and 3-Amino-1-acylethylidene-2-cyanopyrrolizines via Reaction of Acylethynylpyrroles with Malononitrile.

An efficient method for the synthesis of pharmaceutically and high-tech prospective 2-(3-amino-2,4-dicyanophenyl)pyrroles (in up to 88% yield) via the reaction of easily available substituted acylethynylpyrroles with malononitrile has been developed. The reaction proceeds in the KOH/MeCN system at 0 °C for 2 h. In the case of 2-acylethynylpyrroles without substituents in the pyrrole ring, the reaction changes direction: instead of the target 2-(3-amino-2,4-dicyanophenyl)pyrroles, the unexpected formation of pyrrolyldienols and products of their intramolecular cyclization, 3-amino-1-acylethylidene-2-cyanopyrrolizines, is observed.

Catalyst-Free Annulation of Acylethynylpyrroles with 1-Pyrrolines: A Straightforward Access to Tetrahydrodipyrrolo[1,2-a:1',2'-c]imidazoles.

Acylethynylpyrroles undergo facile (rt, MeCN or MeOH, 24-72 h) catalyst-free annulation with 1-pyrrolines to afford acylmethylenetetrahydrodipyrrolo[1,2-a:1',2'-c]imidazoles in up to 93% yield and 90% E-stereoselectivity of the olefin moiety.

Transition metal-free cross-coupling of furan ring with haloacetylenes.

On the example of menthofuran, a naturally abundant compound, it has been shown for the first time that the furan ring can be readily cross-coupled with acylhaloacetylenes in the solid Al2O3 powder at room temperature to afford the corresponding 2-ethynyl derivatives in up to 88% yield. The reaction represents a ring closing/ring opening process that includes reversible formation of the intermediate cycloadducts further producing acetylene derivatives with elimination of HHal.