P. P. Onys'ko

Imidoyl Chlorides: New Promising Building Blocks in Synthesis of α-Aminophosphoryl Compounds

Synthetic and mechanistic aspects relevant to nucleo philic phosphorylation of imidoyl chlorides, their potentialities in preparing functionalized α-aminophosphoryl compounds were discussed.

Sigmatropic Rearrangements in Phosphorylated 2-Azaallylic Systems

Abstract Allylic and heteroallylic compounds are classical objects of organic chemistry and can serve as models in the investigation of various theoretical problems. The anions and 1,3-dipoles generated from azaallylic derivatives are widely used in the synthesis of cyclic and acyclic nitrogen-containing compounds.

Boron trifluoride etherate - an effective catalyst of 1,3-Phosphorotropic migration in CNC triad

A facile BF3·Et2O promoted 1,3-transfer of a diphenylphosphinoyl group in a 2-azaallylic system has been found. The isomerization was shown to proceed by an intramolecular mechanism in the complex formed with participation of a phosphorylated imine PO group.

Methyl trifluoropyruvate diethoxyphosphorylimine

The first example of trifluoropyruvate phosphorylimines was prepared, and its capability for O- and S-amidoalkylation of water, alcohols, and compounds with the SH function was shown. Phenol and 4-methoxyphenol are O-alkylated, while 3-dimethylaminophenol and indole undergo regiospecific C-alkylation at the site of the highest π-electron density.

PHOSPHORYLATED 2-AZAALLYLIC SYSTEMS. SYNTHESIS, PROPERTIES, AND REARRANGEMENTS

Abstract The methods for synthesis of mono- and bisphosphorylated 2-azaallylic compounds were developed. The relevant proto- and phosphorotropic rearrangements in the C=N-C triad were studied.

α—Iminotrifluoroethyl Phosphonates: The First Representatives of C-Phosphorylated N-H Imines

A convenient synthetic approach for previously unknown N-H imidoylphosphonates, based on addition of dialkyl phospites to trifluoroacetonitrile, was developed. Synthetic potentialities of imines 1 existing as equilibrium mixture of E/Z isomers, were demonstrated.

Reaction of N-(Trichloroacetyl)trichloroacetimidoyl Chloride with Phosphites

N-(Trichloroacetyl)trichloroacetylimidoyl chloride reacts with trialkyl phosphites with substitution of the imidoyl chlorine atom and formation of C-phosphorylated heterodienes. The reaction with triphenyl phosphite or o-phenylene diethylphosphoroamidite proceeds as [4+1]-cycloaddition to give mono- or spirocyclic oxazaphospholines with the five-coordinate phosphorus atom. Dialkyl or diphenyl hydrogen phosphites add across the C = N bond of imidoyl chloride to give labile N-(α-phosphorylated) trichloroacetamides.

Synthetic approaches to polyfluorinated α-aminophosphonates

GRAPHICAL ABSTRACT ABSTRACT A convenient synthetic approaches for previously unknown α-aminopolyfluoropropylphosphonic acids derivatives were developed based on readily accessible N-(α-hydroxypolyfluoropropyl)carbamates.

Unprecedented C-Acylation of Imines with Tervalent Phosphorus Isocyanates

Reaction of trifluoropyruvate N-phosphorylimine with tervalent phosphorus isocyanates leads to unexpected acylation of the imine carbon atom to afford phosphorylaminocarbonylated trifluoroalanine derivatives.

Regioselectivity and Sigmatropic Isomerizations in Reactions of Chlorosubstituted Imines with Nucleophiles

Abstract We have shown that the halogen-substituted azomethines reveal different regioselectivity in reactions with nucleophiles.1 The factors determining the ability of the primary reaction products to the 1,3-sigmatropic rearrangements were formulated. The dependence of the regioselectivity of the reactions on the nature of nucleophile and chloroazomethine was discussed. The phosphorus derivatives of azomethines generate 1,3-dipoles under heating giving nitrogen-containing heterocycles in the cycloaddition reactions.