Mikhail Yu. Belikov

Directed synthesis of new spiro-fused photochromes of diarylethene series

The reaction of tetracyanoethylated 1,2-diarylethanones with morpholine was used for directed synthesis of spiro-fused diarylethenes, 8-amino-1-imino(oxo)-6-morpholino-2-oxa-7-azaspiro[4.4]nona-3,6,8-triene-9-carbonitriles. The intermediates in this process were tetracyanoalkanone salts. The formation of spiranes was sensitive to the nature of aromatic substituents at the carbonyl group of 3,4-diaryl-4-oxobutane-1,1,2,2-tetracarbonitriles. The obtained spiro-fused diarylethenes exhibited photochromic properties.

A novel method for the domino synthesis of 6-imino-2,7-dioxabicyclo[3.2.1]octane-4,4,5-tricarbonitriles and studies of stereochemical characteristics of formation and structure thereof

A novel universal method for the preparative synthesis of 6-imino-2,7-dioxabicyclo[3.2.1]octane-4,4,5-tricarbonitriles was developed, previously unknown 1- and 8-aryl-substituted derivatives were synthesized, stereochemical characteristics of this transformation were studied, and the reasons for its diastereoselectivity were identified.

Interaction of 4-oxoalkane-1,1,2,2-tetracarbonitriles with Lawesson's reagent – a new approach to the synthesis of 2,2′-disulfanediylbis(1H-pyrroles). The synthesis of photochromic diarylethene with a disulfide bridge

Transformation of 4-oxoalkane-1,1,2,2-tetracarbonitriles under the action of Lawessons reagent leads to 2,2′-disulfanediylbis(1H-pyrrole-3-carbonitriles) in good yields. The developed method allowed the synthesis of photochromic 2,2′-disulfanediylbis(4,5-bis(2,5-dimethylthiophen-3-yl)-1H-pyrrole-3-carbonitrile).

Directed synthesis of alkyl-substitued pyrrolo[3,4-c]pyrrole-1,3,4,6-tetraones

Reactions of 3-amino-8-hydroxy-1,6-dioxo-2,7-diazaspiro[4.4]non-3-ene-4-carbonitriles with aqueous hydrohalic acid led to the formation of alkyl-substituted pyrrolo[3,4-c]-pyrrole-1,3,4,6-tetraones.

Diastereoselective synthesis of 3,4-dihydro-2H-pyran-4-carboxamides through an unusual regiospecific quasi-hydrolysis of a cyano group

Summary An efficient diastereoselective approach for the synthesis of functionalized 3,4-dihydro-2H-pyran-4-carboxamides with variable frame was developed based on the reaction of available 4-oxoalkane-1,1,2,2-tetracarbonitriles (adducts of TCNE and ketones) with aldehydes in an acidic media. An unusual process of quasi hydrolysis of the cyano group was observed in the course of the described regio- and diastereoselective transformation.

The rare transformation of 2,7-diazaspiro[4.4]nonanes in furo[3,4-c]pyridines

Transformation of 3-amino-8-hydroxy-1,6-dioxo-2,7-diazaspiro[4.4]non-3-en-4-carbonitriles in concentrated hydrohalic acid media leads to the obtaining of two classes of fused heterocycles: 4-halogen-3-hydroxy-1,3-dihydrofuro[3,4-c]pyridin-1-ones and octahydropyrrolo[3,4-c]pyrrole-1,3,4,6-tetraones.

Synthesis of 3H-pyrroles (microreview)

In this microreview, the approaches to the construction of non-condensed 3H-pyrrole ring based mainly on reactions of isonitriles, nitriles, and oximes described in the literature over the past 10 years are presented.

Rearrangement of 4-oxoalkane-1,1,2,2-tetracarbonitriles in the directed synthesis of aryl-substituted 2-(3-cyano-5-hydroxy-1,5-dihydro-2 H -pyrrol-2-ylidene)malononitriles

3-Aryl-4-oxoalkane-1,1,2,2-tetracarbonitriles were synthesized by the interaction of 2-aryl ketones with tetracyanoethylene. Directed rearrangement of them in acetic acid in the presence of ammonium acetate led to the formation of 2-(3-cyano-5-hydroxy-1,5-dihydro-2Hpyrrol-2-ylidene)malononitriles containing an aryl substituent in conjugation with the acceptor buta-1,3-diene-1,1,3-tricarbonitrile moiety.

Three-component synthesis of alkylammonium 4-cyano-5-(dicyanomethylene)-2-hydroxy-2,5-dihydropyrrol-1-ides

This study presents a three-component reaction between malononitrile dimer, α-diketone and aliphatic amine that leads to the formation of previously undescribed alkylammonium 4-cyano-5-(dicyanomethylene)-2-hydroxy-2,3-dimethyl-2,5-dihydropyrrol-1-ides. This reaction is a novel approach for modification of donor–acceptor chromophores containing the buta-1,3-diene-1,1,3-tricarbonitrile moiety.

New approach to the synthesis of 2,3-dihydrofuro[2,3-b]pyridine derivatives: double reduction and double heterocyclization of 2-(3-cyano-5-hydroxy-1,5-dihydro-2H-pyrrol-2-ylidene)malononitriles in the presence of sodium borohydride

The reaction of 2-(3-cyano-5-hydroxy-1,5-dihydro-2H-pyrrol-2-ylidene)malononitriles with an excess of sodium borohydride resulted in diastereoselective formation of 2,3-diaryl-substituted 4,6-diamino-2,3-dihydrofuro[2,3-b]pyridine-5-carbonitriles. This process was accompanied by opening of the pyrrole ring in the starting compounds, followed by a double reduction and tandem closure of furan and pyridine rings.