Mikhail K. Gratchev

THE SYNTHESIS AND STRUCTURE OF P(III)-PHOSPHORYLATED 2-AMINOPYRIDINES AND THEIR DERIVATIVES

Abstract A number of the derivatives of 2-aminopyridine and diisopropyl-phosphinous, neopentylene- and pyr-ocatecholphosphorus acids 1−3 and also the diphosphorylated derivative 4 have been obtained. Phosphinite 1 was alkylated by triethyloxoniumtetrafluoroborate with the formation of quasi-phosphonium salt 5 and was protonated by hydrogen chloride at the endocyclic nitrogen atom to form pyridinium salt 6. The structure of all obtained compounds was studied by 1H, 13C, 15N and 31P NMR spectroscopy and it was shown that they exist predominantly in the phosphoaminopyridine form A.

THIONOPHOSPHATES OF CYCLODEXTRINS

Abstract The preparation of thionophosphates of cyclodextrins by using P(III)-reagents has been investigated.

THE SYNTHESIS AND STRUCTURE OF P(III)-PHOSPHORYLATED 2-AMINOPYRROLINES

Abstract A series of derivatives of 2-aminopyrroline (2-iminopyrrolidine) and neopentylene-, pyrocatecholphosphorous and diisopropylphosphinous acids 5, 11-13, 17, 19 has been synthesized. It was established that P(III)-phosphorylated 2-aminopyrrolines have different structures depending on nature of substituent at the exocyclic N atom: with R[dbnd]Me phosphite 11 is preferably in aminopyrroline form A, with R[dbnd]Ph phosphite 17 is in the iminopyrrolidine form B. The structure of the obtained compounds was studied by means of 1H, 13C, 15N and 31P NMR spectroscopy.

Phosphocontaining Cyclodextrins as a New Class of Supramolecular Structures

Principal peculiarities of the use of phosphocontaining cyclodextrins as a new class of supramolecular structures are discussed. For the first time cyclodextrin perphosphite has been obtained and isolated in an individual state by the treatment of g -cyclodextrin with triazolide neopentylenephosphorous acid. Cyclodextrin perphosphite exhibited an unusual transphosphorylation under reaction with some chlorophosphites. The inclusion of adamantane into the cyclodextrin cavity results in slowing this reaction down. Some water-soluble cyclodextrin derivatives displayed high activity as phase transfer catalysts in biphase catalysis.

Chiral Molecular Cavities on the Basis of Bis-Tetradiamidophosphite of 1,4;3,6-Dianhydro-D-Mannitol

Possibility of creation of chiral molecular cavities on the basis of accessible bisphosphorylated derivative of 1,4;3,6-dianhydro-Dmannitol and bisphenoles of a various nature was investigated. The molecules of bisphosphorylated derivative (I) represent a deepened “basket” possessing a possibility to fix upon itself a “handle,” for example, in the form of a bisphenol residue or diol. Among the investigated bisphenols (HO X OH) only 2,2-di-p-hydroxyphenylpropane, di-p-hydroxyphenyldiphenylmethan, 4,4′-dihydroxyphenyl ether, 4,4′dihydroxyphenylsilfide turned out to be the suitable models for the creation of phosphocontaining macroheterocyclic structures (II) on the basis of D-mannitol derivative (I).

New Chiral Phosphocontaining Heterocycles on the Basis of Natural Oligohydroxyl Compounds

Principal possibilities of creation of chiral phosphocontaining heterocycles on the basis of natural derivatives of cyclodextrins and dianhydro-D-mannitol are discussed. The obtained compounds possess an internal chiral cavity of a definite size and represent an interest for the solution of modern tasks of biomimetic and supramolecular chemistry.

Investigation of Phosphorylation of Cyclodextrins and Some their Derivatives

Abstract Principal regularities of per- and regodirected phosphorylation of α-β-, and γ-cyclodextrins (R=R1=R2=OH, n= 1–3) by trivalent phosphorus reagents were investigated. As a result, the first representatives of regularly organized phosphites and amidophosphites of cyclodextrins, including ones with interglucoside 2,3′-cyclophosphite bridges [R1+R2=-P(NR2′)-], having chiral cavities of different sizes, were obtained. Per-6-deoxy-6-bromocyclodextrins (R=Br) were considered as convenient intermediates for the synthesis of pyndinium salts with amphiphilic properties for the enhanced water-solubility and for the definite orientation at the phase boundary organic liqiud-water.

P(Iii)-Amines as Phosphorylating Agents for Alcohols and Amines. Modern Aspect of the Problem.

Abstract The factors governing the reactivity of P(III)-amines towards protonodonor nucleophiles are discussed. The last data on mechanism of acid catalysis, intramolecular catalysis and possibility of stereoselective phosphorylation by phosphoroamidites are represented.

Chiral Oligo- and Polyphosphites (Phosphonites, Phosphinites) on the Base of Specifically Orientated in Space Hydroxylcontaining Compounds. Synthesis, Structure, and Investigation of Complexation

Abstract The effective methods of phosphorylation of complex systems with specifically orientated in space hydroxyl groups, namely dianhydro-D-mannitol(A), -D-sor-bitol(B), cyclodextrines(C), and cellulose(D) (A-D, where R=H), have been elaborated.

Catalytic Activity of Amines Hydrochlorides, Intramolecular Catalysis and Stereoselectivity of Phosphorylation of Hydroxylcontaining Nucleophiles with P(III)-N-Ethylanilines

Abstract The effect of acid-base properties of amines hydrochlorides (AH) on their catalytic activity in methanolysis of P(III)-N-ethylaniline has been studied. The analysis of Bronsted correlation equation was indicative of general acid catalysis and it was thus confirmed, that general regularities had place during alcoholysis of P(III)-amines under catalysis with AH. In addition, the increasing of alcohol polarity leads to the increasing of proton transfer degree (α) from acid catalysts to phospho(III)amine substrate and to the increasing of the positive charge at the phosphorus in the transition state. Besides, the comparison of α values indicates that in more polar methanol (in comparison with tbutanol) the catalysis is more sensitive to the acidity change of used catalysts.