Sibgatulin D. Synthesis and properties of C-beta'-functionalized enamines

The dissertation is devoted to studying reactions of push-pull enamines having a methyl group at the alfa-position with mono- and bielectrophilic reagents. It was shown that the linear push-pull enamines react with a set of mono- and bielectrophilic reagents at the methyl group affording beta'-functionalized derivatives. Presence of a strong electron-acceptor substituent at trifluoromethylketones was shown to play an important role in the reaction. Systematic investigation of the reaction of the push-pull enamines with ethyl trifluoroacetoacetate and trifluoroacetoacetone allowed us to propose a convenient method for synthesizing trifluoromethyl-containing aromatic compounds. The enamines derived from derivatives of 1,3-dicarbonyl compounds react with ethyl trifluoroacetoacetate affording cyclic products - derivatives of trifluoromethyldialkylanilines. It should be noted that it is the very first example of enamines reacting as 1,4-CCCC synthon. The reaction of the enamines with imines of methyl trifluoropyruvate proceeds at the beta'-position thus providing a new synthetic approach to aminoalkylated derivatives of the push-pull enamines. These compounds easily hydrolyze to the corresponding carbonyl derivatives and were successfully used for the synthesis of trifluoromethyl hetaryl alanines.