Dibenzoate esters of cis-tetralin-2,3-diol as analogs of (-)-epigallocatechin gallate: synthesis and crystal structure of anticancer drug candidates.

(-)-Epigallocatechin gallate (EGCG), the main component of green tea extract, displays multiple biological activities. However, it cannot be used as a drug due to its low cellular absorption, instability and metabolic degradation. Therefore, there is a need to provide analogs that can overcome the limitations of EGCG. In this work, six synthetic analogs of EGCG sharing a common tetralindiol dibenzoate core were synthesized and fully characterized by 1H NMR, 13C NMR, HRMS and IR spectroscopies, and X-ray crystallography. These are (2R,3S)-1,2,3,4-tetrahydronaphthalene-2,3-diyl bis[3,4,5-tris(benzyloxy)benzoate], C66H56O10, and the analogous esters bis(3,4,5-trimethoxybenzoate), C30H32O10, bis(3,4,5-trifluorobenzoate), C24H14F6O4, bis[4-(benzyloxy)benzoate], C38H32O6, bis(4-methoxybenzoate), C26H24O6, and bis(2,4,6-trifluorobenzoate), C24H14F6O4. Structural analysis revealed that the molecular shapes of these dibenzoate esters of tetralindiol are significantly different from that of previously reported dimandelate esters or monobenzoate esters, as the acid moieties extend far from the bicyclic system without folding back over the tetralin fragment. Compounds with small fluorine substituents take a V-shape, whereas larger methoxy and benzyloxy groups determine the formation of an L-shape or a cavity. Intermolecular interactions are dominated by π-π stacking and C-H...π interactions involving the arene rings in the benzoate fragment and the arene ring in the tetrahydronaphthalene moiety. All six crystal structures are determined in centrosymmetric space groups (either P-1, P21/n, C2/c or I2/a).

Syntheses, characterization, and antitumor activities of platinum(II) and palladium(II) complexes with sugar-conjugated triazole ligands.

Four platinum(II) and palladium(II) complexes with sugar-conjugated bipyridine-type triazole ligands, [Pt(II)Cl(2)(AcGlc-pyta)] (3), [Pd(II)Cl(2)(AcGlc-pyta)] (4), [Pt(II)Cl(2)(Glc-pyta)] (5), and [Pd(II)Cl(2)(Glc-pyta)] (6), were prepared and characterized by mass spectrometry, elemental analysis, (1)H- and (13)C-NMR, IR as well as UV/VIS spectroscopy, where AcGlc-pyta and Glc-pyta denote 2-[4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl]ethyl 2,3,4,6-tetra-O-acetyl-ß-D-glucopyranoside (1) and 2-[4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl]ethyl ß-D-glucopyranoside (2), respectively. The solid-state structure of complex 6 was determined by single-crystal X-ray-diffraction analysis. These complexes exhibited in vitro cytotoxicity against human cervix tumor cells (HeLa) though weaker than that of cisplatin.

Redox-controlled, reversible rearrangement of a tris(2-pyridylthio)methyl ligand on nickel to an isomer with an "N,S-confused" 2-pyridylthiolate arm.

Interchange between the nickel +2 and +3 oxidation states precisely controls the reversible rearrangement of the tris(2-pyridylthio)methanide (tptm) ligand in the organometallic nickel(II) complex [{Ni(µ-Br)-(tptm)}(2)] (2). Oxidation of 2 first gives the corresponding Ni(III) complex [{Ni(µ-Br)(tptm)}(2)][PF(6)](2) (4). However, in solution the tptm ligand in 4 slowly undergoes a rearrangement, in which the N and S atoms of one of the pyridylthiolate arms exchange Ni and C bonding partners, thereby resulting in an "N,S-confused" isomer of tptm in the product, [NiBr(bpttpm)]PF(6) (5; bpttpm= bis(2-pyridylthio)(2-thiopyridinium)-methyl). Reduction of 5 reverses this ligand rearrangement and 2 is reformed quantitatively. The individual steps involved in these unusual ligand rearrangements were investigated by a number of methods, including voltammetric analysis, and a mechanism for this process is proposed. X-ray crystal structure determinations of the key compounds 2, 4 and 5 have been obtained.

Dynamic behaviour attributed to chiral carbohydrate substituents of N-heterocyclic carbene ligands in square planar nickel complexes.

Nickel complexes having acetylated glucopyranosyl group incorporated N-heterocyclic carbene (NHC) ligands with methyl or benzyl groups as an N-substituent exhibit two kinds of dynamic behaviours in solution (1)H NMR spectroscopy. One of the dynamic behaviours is attributed to the anti- and syn-rotamers, which occur by the rotation of the unsymmetrical NHC ligands around the axes of the Ni-C bonds. The other is attributed to the diastereomers of the syn-rotamers, which occur by opposite rotation of the imidazolylidene rings and the chiral carbohydrate group incorporated into the NHC ligands. Crystallographic analysis of the nickel complex having the NHC ligand with acetylated glucopyranosyl and benzyl groups as N-substituents showed CH-π interaction between the glucopyranosyl unit of each NHC ligand and the phenyl ring of the other NHC ligand in the complex in the solid state.

Carbon-sulfur bond cleavage reactions of dibenzothiophene derivatives mediated by iron and ruthenium carbonyls.

A thermal reaction of 6-(4''-dibenzothienyl)-2,2'-bipyridine (bpyDBT) with [Ru(3)(CO)(12)] produced a sulfur-bridged triruthenium complex via double carbon-sulfur bond cleavage and CO insertion, while a diiron(I,I) complex containing a thiametallacycle was obtained by a photochemical reaction of bpyDBT with [Fe(CO)(5)].

Rh(I)-catalyzed CO gas-free carbonylative cyclization reactions of alkynes with 2-bromophenylboronic acids using formaldehyde.

The rhodium(I)-catalyzed reaction of alkynes with 2-bromophenylboronic acids in the presence of paraformaldehyde resulted in a CO gas-free carbonylative cyclization, yielding indenone derivatives. [RhCl(BINAP)](2) and [RhCl(cod)](2) were responsible for the decarbonylation of formaldehyde and the subsequent carbonylation of alkynes with 2-haloboronic acids, respectively, leading to efficient whole carbonylation. Sterically bulky and electron-withdrawing groups on unsymmetrically substituted alkynes favored the alpha-position of indenones.

Catalytically active mu-Oxodiiron(IV) oxidants from Iron(III) and dioxygen.

The reaction between an Fe(III) complex and O(2) to afford a stable catalytically active diiron(IV)-mu-oxo compound is described. Phosphonium salts of orange five-coordinated Fe(III)-TAML complexes with an axial aqua ligand ([PPh(4)]1-H(2)O, tetraamidato macrocyclic Fe(III) species derived from 3,3,6,6,9,9-hexamethyl-3,4,8,9-tetrahydro-1H-1,4,8,11-benzotetraazacyclotridecine-2,5,7,10(6H,11H)-tetraone) react rapidly with O(2) in CH(2)Cl(2) or other weakly coordinating solvents to produce black mu-oxo-bridged diiron(IV) complexes, 2, in high yields. Complexes 2 have been characterized by X-ray crystallography (2 cases), microanalytical data, mass spectrometry, UV/Vis, Mossbauer, and (1)H NMR spectroscopies. Mossbauer data show that the diamagnetic Fe-O-Fe unit contains antiferromagnetically coupled S = 1 Fe(IV) sites; diamagnetic (1)H NMR spectra are observed. The oxidation of PPh(3) to OPPh(3) by 2 was confirmed by UV/Vis and GC-MS. Labeling experiments with (18)O(2) and H(2)(18)O established that the bridging oxygen atom of 2 derives from O(2). Complexes 2 catalyze the selective oxidation of benzylic alcohols into the corresponding aldehydes and bleach rapidly organic dyes, such as Orange II in MeCN-H(2)O mixtures; reactivity evidence suggests that free radical autoxidation is not involved. This work highlights a promising development for the advancement of green oxidation technology, as O(2) is an abundant, clean, and inexpensive oxidizing agent.