I. M. Aladzheva

Palladium(II) Chloride Interaction with Chelating BIS(Phosphine Sulfides). Effect of the Ligand Structure on the Complex Geometry

Abstract Interaction of PdCl2 in chloroform with bis(phosphine sulfides) Ph2P(S)‒X‒P(S)Ph2 (X‒CH2, C(CH3)2, CH2CH2, NH, S, and SCH2S) has been studied. Mechanism of the reaction has been found to vary dramatically with the identity of X. The structures of the resultant complexes were evaluated by UV and IR spectroscopy. Crystal structures were were determined by X-ray diffraction for two of the compounds (A: [Ph2P(S)‒(CH2)2‒P(S)Ph2]PdCl2 · CH3CN, P21/n, Z = 4, a = 10.104(2), b = 20.939(4), c = 14.034(3) Å, γ = 102.54(2)· B: [Ph2P(S)‒N‒P(S)Ph2]2Pd · 2CHCl3, Pl, Z = 1, a = 9.539(1), b = 12.333(3), c = 12.866 Å, α = 111.83(2)°, β = 96.70(3)° γ = 99.84(3)°).

Catalytic activity of new PdII-complexes of bidentate PIII—N—PIII-ligands in Suzuki—Miyaura reaction

A reaction of readily available bis(diphenylphosphino)amines with (PhCN)2PdCl2 was used to synthesize PdII-complexes [Pd{Ph2PN(R)PPh2}Cl2] (R = Pri, cyclo-C6H11, Ph), which exhibited a high activity in the cross-coupling of aryl bromides with phenylboronic acid.

Pishchimuka's Intramolecular Rearrangement. The General Method for the Synthesis of 2-Oxo-1,2λ5-thiaphoapholanes and Thiaphosphorinanes

A new method is developed for the synthesis of 2-substituted 2-oxo-1,2λ5-thiaphospholanes and thiaphosphorinanes (thiolphostones) on the basis of intramolecular Pishchimuka rearrangement of thiophosphonic and thiophosphinic esters with ω-chloroalkyl substituents at the phosphorus atom. Intermediate compound in the Pishchimuka rearrangement, 2-ethyl-2-ethoxy-1,2λ4-thiaphospholanium perchlorate, was isolated.

Alkylation of Hydrothiophosphoryl Compounds by Digalogenoalkanes Under Phase Transfer Caralysis Conditions

Abstract The course of reactions of hydrothiophosphotyl compounds with dihalogenoalkanee under PTC conditions depends both on the nature of halogen atom and the length of the alkylene chain.I reacts with CH2Br2 to yield Ph2P(S)CH3; with ICH2Cl Ph2P(S)CH2Cl is formed.

NEW COMPLEXES OF PALLADIUM(II) CHLORIDE WITH CHELATING PHOSPHORUS, SULFUR CONTAINING LIGANDS

Abstract New palladium(II) coordination compounds PdLCl2 and PdL2Cl2 with chelating ligands containing thiophosphoryl groups along with carbamoyl or thiocarbamoyl groups were synthesized. The structures of the complexes in solutions and in solid were studied by electronic and IR spectroscopy, conductometry, and FD mass spectrometry. Transformations of the complex PdL3 2Cl2 under a strong electric field were investigated.

Synthetic Approaches to 1,2-Heteraphosphacyclanes

1,2-Heteraphosphacyclanes have drawn the attention of synthetic chemists due to their association with various biological activities and their unusual properties. The focus of this chapter is on the synthetic approaches to heterocyclic compounds of this type, which are principally different from the compounds with three-membered, four-membered and larger ring size and differ greatly depending on the nature of the heteroatom in the ring.

Prototropic Tautomerism in Phosphoryl-Hydroxyylide and Thiophosphoryl-Mercaptoylide Systems

Abstract Two new types of tautomerism are discussed: phosphoryl-hydroxyylide and thiophosphoryl-mercaptoylide tautomerism.

Synthesis of precursors to new tripodal phosphine oxide ligands

A number of precursors of new tripodal ligands was obtained by hydroxyethylation of the starting tris(2-hydroxyphenyl)phosphine oxide, followed by conversion of the resulting tris[2-(2-hydroxyethoxy) phenyl]phosphine oxide to trimesylate. The treatment of the latter with LiBr or NaN3 afforded the corresponding tribromo and triazido derivatives.

Synthesis and study of antitumor activity of 4 H -pyrano[3,2- c ]pyridines based on N -(2-azidoethyl)- and N -propargyl-3,5-bis(arylidene)piperidin-4-ones

The synthesis of 3,5-bis(arylidene)piperidin-4-ones containing the 2-azidoethyl (azides 1a–d) or propargyl (acetylenes 2a–c) group at the nitrogen atom of the 4-piperidinone ring was described. The in vitro MTT assay for cytotoxicity of these compounds toward the human tumor cell lines PC3, HCT116, and MCF7 and the human embryonic kidney cells HEK293 revealed that N-(2-azidoethyl)-3,5-bis(3-pyridylidene)piperidin-4-one (1c) and N-propargyl-3,5- bis(benzylidene)piperidin-4-one (2a) exhibit high activity (IC50 in the range of 1–5 μmol L–1). The reaction of compounds 1a–d and 2a–c with malononitrile affords the corresponding 4H-pyrano[3,2-c]pyridines 3a–d and 4a–c devoid of cytotoxicity. This is evidence of the importance of preserving the 1,5-diaryl-3-oxo-1,4-pentadiene moiety upon the modification of 3,5-bis(arylidene)piperidin-4-ones in drug design when searching for new antitumor agents based on these compounds.

Phase-transfer Tsuji—Trost allylation of CH-acids with the assistance of palladium complexes with bidentate P III —N—P III ligands

The Tsuji—Trost allylation of CH acids, in particular, those of the YCH2CO2Et type (Y = CO2Et, C(O)Me, CN), with allylic acetates in the K2CO3—DMF system in the presence of palladium catalysts with ligands RN(PPh2)2 (R = Ph, Pri, c-C6H11) is accomplished.