Cyclopalladation of the indole ring in palladium(II) complexes of 2N1O-donor ligands and its dependence on the O-donor properties

Synthetic, structural, spectroscopic, and kinetic studies have been carried out on the Pd(II) complexes of new 2N1O-donor ligands containing a pendent indole, 3-(N-2-pyridylmethyl-N-2-hydroxy-5-methoxybenzylamino)ethylindole (HMeO-iepp), 3-(N-2-pyridylmethyl-N-2-hydroxy-5-nitrobenzylamino)ethylindole (HNO2-iepp), and (N-2-pyridylmethyl-3-indolylethylamino)acetic acid (Hiepc) (H denotes a dissociable proton). [Pd(MeO-iepp)Cl] (2), [Pd(NO2-iepp)Cl] (3), and [Pd(iepc)Cl] (4) were prepared and revealed by X-ray analysis to have a pyridine nitrogen, an amine nitrogen, a phenolate or carboxylate oxygen, and a chloride ion in the coordination plane. UV absorption and 1H NMR spectral changes indicated that all the complexes could be converted to the indole-binding complexes where the O donor was replaced by the indole C2 atom by cyclopalladation in DMSO or DMF in the temperature range of 40-60 degrees C. Formation of the indole-binding complex species obeyed the first-order kinetics, from which the activation parameters were estimated. The formation rate was dependent on the properties of the O-donor group, a lower pKa value of its conjugate acid causing faster conversion to the indole-binding species in the order 2 (methoxyphenolate) < 3 (nitrophenolate) < 4 (carboxylate). On the other hand, the ratio of the indole-binding complex to the O-donor complex as a result of the conversion was greater for the complexes with a higher pKa value of the ligand OH group, the order being 2 > 3 > 4.     

Synthesis of spirodienones by intramolecular ipso-cyclization of N-methoxy-(4-halogenophenyl)amides using [hydroxy(tosyloxy)iodo]benzene in trifluoroethanol

Spirodienones bearing the 1-azaspiro[4.5]decane ring system have been synthesized from N-methoxy-(4-halogenophenyl)amides by the intramolecular ipso attack of a nitrenium ion generated with [hydroxy(tosyloxy)iodo]benzene in trifluoroethanol.     

New reactions of 1-alkynes catalyzed by transition metal complexes

Recently discovered catalytic reactions with ruthenium and lanthanide metal complexes have extended the scope of 1-alkynes as useful reagents. The specific formation of aryl-substituted (Z)-1,3-enzymes via the dimerization of HC(triple bond) CR(1) (R(1) = aryl) has been attained using dimeric lanthanide complexes, the catalytic activity of which appears to be unaffected by time. The dimerization of HC(triple bond) CR(2) (R(2) = t-Bu, SiMe(3)) catalyzed by Ru(cod)(cot)/PR(3) or RuH(2)(PPh(3))(3) produces a good yield of butatrienes (Z)R(2)CH=C=C=CHR(2) with a high degree of selectivity. Under certain conditions, HC(triple bond) C=SiMe(3) dimerizes to yield exclusively (Z)-M(3)Si-C(triple bond) C-CH=CH-SiMe(3). The hydration of HC(triple bond)CR(3) (R(3) = alkyl, aryl) catalyzed by RuCl(2)/PR'(3) or CpRuCl(PR"(3))(2) has realized the first example of anti-Markovnikov regioselectivity in an addition reaction of water that produces aldehydes R(3)CH(2)bond;CHO. The application of this reaction to propargylic alcohols has lead to their formal isomerization to alpha,beta-unsaturated aldehydes. In contrast, the addition of amines R(4)bond;NH(2) (R(4) = aryl) to HCtbond;CR(5) (R(5) = alkyl, aryl) conforms to Markovnikov's rule to produce ketimines R(5)bond;(C=NR(4))bond;CH(3) when catalyzed by a Ru(3)(CO)(12)/additive. Since the reaction can be performed in air without the need for any solvents, it enables the practical synthesis of aromatic ketimines, which are difficult to prepare by conventional methods. The synthesis of indoles using deactivated anilines is one practical application of this reaction. The mechanisms of some of these reactions have been analyzed in detail with the aid of theoretical calculations.     

Preparation and characterization of novel polyaryloxydiphenylsilanes with high glass transition temperature by melt polycondensation of dianilinodiphenylsilane with bisphenols

Novel polyaryloxydiphenylsilanes with reduced viscosities of 0.31–0.65 dL/g were obtained by the melt polycondensation of dianilinodiphenylsilane with three bisphenols, 2,2-bis (4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 3 (4-hydroxyphenyl)-1,1,3-trimethyl-5-indanol, and 9,9-bis (4-hydroxyphenyl) fluorene, at 200–320°C in vacuo. These polymers are all amorphous and readily soluble in a wide variety of organic solvents such as chlorinated and aromatic hydrocarbons, cyclic ethers, and polar aprotic solvents. Because of their bulky and/or rigid ring structures, polyaryloxydiphenylsilanes containing diphenylhexafluoropropane, phenylindane, and diphenylfluorene units in the main chain have high glass transition temperatures of 106, 112, and 172°C, respectively. They are thermally stable showing almost no weight loss up to 350°C in air. Colorless, transparent, but brittle films are obtained from these polymers by solution casting. Ultraviolet transmission is sharply cut off by these polyaryloxydiphenylsilane films at ca. 300 nm, and the cut-off wavelength depends on the bisphenols used.     

Conductive characteristics of radical‐bearing polythiophenes using a microcomb‐shaped electrode

The electric conductivity of π‐conjugated and radical‐bearing polymers, i.e., polythiophenes bearing pendant galvinoxyl and phenoxyl radical groups, was measured using a microcomb‐shaped electrode. The electric conductivity was found to be enhanced by the radical content in the polymer. The infrared (IR) and Raman spectroscopies suggested a structural change from an aromatic form to a quinoid one in the polythiophene backbone by the phenoxyl radical generation. The effect of the pendant galvinoxyl radical's unpaired electron on the electric conductivity of the polythiophene was discussed by comparing the conductivity of a radical‐bearing polystyrene and a polythiophene mixed with low‐molecular radical molecules. Copyright © 2007 John Wiley & Sons, Ltd.     

Analysis of oxidized epigallocatechin gallate by liquid chromatography/mass spectrometry

(-)-Epigallocatechin gallate (EGCG) of catechins changes from non-colored at around neutral pH to yellow at higher pH region in aqueous solution. The pH-dependent oxidation of EGCG was analyzed by liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS). LC/MS/MS analysis of EGCG and its related compounds, (-)-epicatechin gallate (ECG) and (-)-epigallocatechin (EGC), successfully elucidated the structure relationship of EGCG solution involving the color change reaction at different pH conditions. The oxidation species produced at alkaline pH was detected at a different retention time from EGCG in the chromatograms of the EGCG sample. The oxidation species was found to correspond to M+14 (where M is the molecular weight of EGCG), which has two hydrogen atoms removed and addition of one oxygen atom to the gallyl moiety in the B-ring of EGCG.     

Polymerization of bis(2-oxazoline) compounds with dicarboxylic acids

A side reaction was found in the reaction of a 2-oxazoline compound with a carboxylic acid. It is an oxazoline ring opening addition to an amide group formed by the main reaction. In addition, certain phosphites were found to act as catalyst for the side reaction. The rate constants of the main and side reactions in the system of 2-phenyl-2-oxazoline and n-octanoic acid were obtained through simulation of the reactions on an analog computer. The side reaction makes it impossible for a very high molecular weight polymer to form in the reaction of a bis-2-oxazoline with a dicarboxylic acid, but makes it possible for a new crosslinked polymer to form when excess bis-2-oxazoline and a dicarboxylic acid are heated in the presence of a certain phosphite.     

Hydroxylation of ionized aromatics including carboxylic acid or amine using recombinant Streptomyces lividans cells expressing modified biphenyl dioxygenase genes

The bphA1(2072)A2A3A4 gene cluster codes for a shuffled biphenyl dioxygenase holoenzyme with broad substrate specificity. These bphA1(2072)A2A3A4 genes were expressed in the actinomycetes Streptomyces lividans using a thiostrepton-inducible promoter P_tipA. Biotransformation experiments of various aromatics including carboxylic acid or amine in their molecular structure, such as 1-naphthoic acid, 2-(1-naphthyl)acetic acid, diphenylamine, and 1-benzyl-4-piperidone, were performed using the recombinant S. lividans cells. These ionized aromatics were converted to the corresponding 1,2-dihydrodiol, mono- or tri-hydroxy forms in 48 h. The structure of the converted products was determined by their EI-MS, ¹H- and ¹³C NMR analysis, and several products were found to be novel compounds.     

Alternating copolymerization of isoprene and butadiene with acrylonitrile

Copolymerizations of acrylonitrile and isoprene or butadiene were carried out in the presence of a new catalytic system containing Cr(O-tert-Bu)₄ and AlEtCl₂. It was found that the copolymer compositions have a highly alternating structure, even with varying feed ratios of monomer. The nuclear magnetic resonance spectra of the copolymers obtained with this catalytic system were observed and are discussed in terms of the alternation.     

Synthesis of aromatic polythioamide-oxothioxoquinazolines from bis(1,3,4-thiadiazoline-5-thione) and aromatic bis-o-amino esters

Aromatic polythioamide-oxothioxoquinazolines were synthesized by the polycondensation of 2,2′-(m-phenylene)bis-1,3,4-thiadiazoline-5-thione with aromatic bis-o-amino esters. The polymerizations were carried out at 160°C in acidic media such as m-cresol, sulfolane, and polyphosphoric acid to produce polymers with reduced viscosities up to 0.5 dL/g. These polymers were soluble in polar aprotic solvents like N-methyl-2-pyrrolidone and some acidic media including m-cresol. The polythioamide-oxothioxoquinazolines showed relatively good thermal stability with 10% weight loss at 344–394°C in air.