Yuliya V. Rassukana

Synthesis and rearrangements of N-trichloroacetylfluoroacetimidoyl chloride and its phosphorylation products

Abstract The interaction of N -fluoroacetyltrichloroacetamide ( 1 ) with PCl 5 leads to the formation of N -trichloroacetylfluoroacetimidoyl chloride ( 3 ), which is irreversibly isomerized to N -chloro(fluoro)vinyltrichloroacetamide ( Z / E ≈3:1) in the presence of the catalyst DBU. In the reaction of 3 with phosphites or phosphines, the substitution of chlorine atom by the phosphorus-containing groups is accompanied by the stereoselective 1,3-H transfer affording C-phosphorylated fluorovinylamides ( 6 , 9 ), mainly with the E -configuration. With low-nucleophilicity phosphites, there is realized the [4+1]-cycloaddition, whereas with hydrophosphoryl reagents, the 1,2-addition to the CN bond occurs.

A new reaction of vicinal sulfonyliminocarboxylates with phosphites

Abstract The reaction of alkyl trifluoro(organylsulfonylimino)propionates with phosphites occurs with NC transfer of the RSO2 group and leads to sulfonyl-substituted trifluoroalanine derivatives. The novel rearrangement is interpreted as cheletropic 1,4-cycloaddition of the phosphite and subsequent 1,2-shift of the sulfonyl group in the intermediate cyclic phosphorane.

Phosphite Mediated Heterocyclization of Fluorinated Heteryliminophosphonates and Carboxylates

Abstract Phosphite-induced heterocyclization of (N-heterylimino)-trifluoroethyl phosphonates and carboxylates leads to novel fused imidazoles of biological relevance, bearing fluorine atom and phosphonyl or carboxyl function in neighboring positions of imidazole ring. GRAPHICAL ABSTRACT

A New Strategy for Synthesis of Compounds Bearing Biorelevant α-Aminophosphonate Functionalities

GRAPHICAL ABSTRACT Abstract A novel strategy for synthesis of biorelevant α-aminophosphonic acid derivatives, based on the use of α-iminophosphonates as starting materials, was developed.

Phosphorylation of Imino Analogs of α -Halocarbonyl Compounds

Phosphorylation of the α-haloimines leads mainly to C- or N-phosphorylated compounds as the final products, and selectivity being dependent on the type of halogen, substituents at the imine carbon and nitrogen atoms, and on the nature of phosphorus regeant. Variety of transformations is connected with rearrangements accompanied by umpolung of C- and N-center of imine function, possible participation of C═N bond, halogen atoms or N-substituents, in ractions involving the Hal-C─C═N skeleton.

Dimenthoxyphosphorylimino-3,3,3-trifluoropropionate as a Novel Chiral Building Block in Asymmetric Synthesis of Fluorinated α-Amino Acids Derivatives

Abstract A convenient method for the preparation of dimenthoxyphosphoryliminotrifluoropropionate, bearing the stereodirecting dimenthoxy-phosphoryl group at the nitrogen atom, was developed. The synthetic potential of this novel chiral building block for diastereoselective synthesis of trifluoromethyl containing amino acid derivatives was demonstrated.