Laboratory of azapolyene and ylide intermediates

Compounds with small nitrogenous heterocycles are of interest not only as convenient synthetic blocks in the design of nitrogen-containing compounds, but also as potential pharmaceuticals. We are searching for synthetic approaches to new biologically active compounds of a number of azirine, aziridine and azet, in particular, such as derivatives of azirine carboxylic acids, azirine-containing dipeptides and depsipeptides, derivatives of dihydroazet carboxylic acids.

The development of any synthetic method involves clarifying the mechanism of the reaction underlying it. The latest works of the scientific group present quantum chemical substantiations of the mechanisms of the following new reactions: cascade SN2'-SN2' nucleophilic substitution in the azirine cycle; rhodium-catalyzed triazole-triazole and triazole-pyrazole combination; rhodium-catalyzed transanneling of 1,2,3-triazoles by diazo compounds; acid-catalyzed rearrangement into 1-acyl-2-azabute-1,3-dienes; TBTH-promoted ionic 5-exo-trig cyclization of 5-chloro-3-azamuconoates. Quantum chemical modeling of new reactions of metallocarbenes, metallonitrenes and N-ylides helps not only to intelligently plan the synthesis of new compounds, but also to discover new reactions.

A series of studies is being conducted to develop new methods for the production of synthetically and pharmacologically significant 5-6-membered nitrogenous heterocyclic scaffolds based on reactions of azirines, diazo compounds and 1,2,3-triazoles under conditions of catalysis by transition metals and, above all, copper, rhodium and gold compounds.

Conjugated azapolyenes are an extremely interesting and synthetically very promising class of nitrogen—containing compounds that are currently undergoing rapid development. Taking advantage of the unusually high propensity of these compounds to pericyclic transformations, not only monocyclic nitrogenous structures of almost any size can be easily obtained from them, but also unique bridging bicyclic systems with high atom economy and selectivity can be formed from them in one synthetic stage.