Mikhail Yu. Ievlev

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.

Diastereoselective Cascade Assembly of Functionalized Pyrano[3,4-c]pyrrole Derivatives

A novel convenient approach for the synthesis of densely functionalized pyrano[3,4-c]pyrrole derivatives was developed. Cascade transformation of the simple adducts of tetracyanoethylene (TCNE) and ketones (4-oxoalkane-1,1,2,2-tetracarbonitriles) in the presence of aldehyde under the action of acetic acid led to the diastereoselective formation of targeted pyrano[3,4-c]pyrroles. The reaction pathway was thoroughly investigated, and proposed intermediates were shown to be consistent with experiment.

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).

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.

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.

Iminolactone-lactam rearrangement in reactions of γ-oxonitriles

This minireview describes the reactions of γ-oxonitriles with various nucleophiles, accompanied by rearrangement of intermediates containing iminolactone ring to lactams, which have been reported in the literature over the last 10 years.

Synthesis of 2,7-dioxabicyclo[3.2.1]octanes (microreview)

Methods of synthesis of 2,7-dioxabicyclo[3.2.1]octanes published over the past 10 years are summarized. Current methods for constructing the 2,7-dioxabicyclic system are of the following types: annulation of a new ring to an existing pyran or furan ring, tandem closing of both rings in differing order in one synthetic step, as well as recyclization and (3+3) cycloaddition reactions.

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.

Synthesis of pyrano[3,4- c ]pyrroles (microreview)

This microview compiles approaches to the synthesis of derivatives of pyrano[3,4-c]pyrrole not condensed with other cyclic fragments covered in the literature starting from 2007.