Petro P. Onys’ko

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.

N-(R-Cyclopropyl) Trifluoroacetimidoyl Phosphonates

Abstract A convenient synthetic approach for previously unknown N-(R-cyclopropyl)trifluoroacetimidoyl phosphonates 5a,b (R˭H, CF3) was developed on the basis of the reaction of respective trifluoroacetimidoyl chlorides with triethyl phosphite. It was shown that imidoyl phosphonates 5a,b exist as equilibrium mixture of Z/E isomers (Z:E ∼92:8). Activation parameters of Z–E isomerization were evaluated by 19F NMR spectroscopy. Catalytic hydrogenation of 5a,b can serve as a convenient method for the synthesis of trifluoroethylaminophosphonates with a rigid N-cyclopropyl group. GRAPHICAL ABSTRACT

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.

CCDC 1444368: Experimental Crystal Structure Determination

Related Article: Alexander A. Shalimov , Tetyana I. Chudakova, Yurii G. Vlasenko, Anatoly D. Sinitsa, Petro P. Onys’ko|2016|Chemistry of Heterocyclic Compounds|52|267|doi:10.1007/s10593-016-1873-z

CCDC 1444371: Experimental Crystal Structure Determination

Related Article: Alexander A. Shalimov , Tetyana I. Chudakova, Yurii G. Vlasenko, Anatoly D. Sinitsa, Petro P. Onys’ko|2016|Chemistry of Heterocyclic Compounds|52|267|doi:10.1007/s10593-016-1873-z

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.