Cobalt(II) chloride as a novel and efficient catalyst for the synthesis of 1,2,5‐trisubstituted pyrroles under solvent‐free conditions

CoCl₂ is used as an efficient catalyst in the Paal–Knorr condensation of 2,5‐hexadione with primary amines under solvent‐free conditions, leading to the formation of pyrrole derivatives in excellent yield. This method is very easy, rapid, and high yielding reaction for the synthesis N‐substituted pyrrole derivatives. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:592–595, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20482     

The first stereospecific arylation of (Z)‐germyl(stannyl)ethenes with an aryl halide or heteroaryl halide under palladium‐catalysis

A combination catalyst of Pd(dba)₂‐PPh₃‐CuI‐LiCl or Pd(dba)₂‐P(2‐furyl)₃‐CuI‐LiCl effectively catalyzed the cross‐coupling of (Z)‐germyl(stannyl)ethenes with aryl halides, providing novel triethyl(2,2‐diarylethenyl)germanes in good to high yields. The reaction proceeds with retention of configuration. Cross‐coupling results in the formation of phenylene or phenyleneethynylene derivatives with terminal stereochemically defined vinylgermane unit(s). Copyright © 2008 John Wiley & Sons, Ltd.     

A convenient synthesis of 2‐(1H‐1,2,4‐triazol‐1‐yl)‐2H‐1,4‐benzothiazine derivatives

A series of 2‐(1H‐1,2,4‐triazol‐1‐yl)‐2H‐1,4‐benzothiazines were designed and synthesized by condensation of 1,2,4‐triazole‐substituted ω‐bromoacetophenones and o‐aminothiophenols with the aid of K₂CO₃ under mild conditions with moderate to high yields. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:332–336, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20434     

Thermally latent synthesis of networked polymers from multifunctional hemiacetal ester and diepoxide catalyzed by Schiff‐base‐zinc chloride complex

Thermally latent reaction of a copolymer ( P1 ) bearing hemiacetal ester and n‐butyl methacrylate moieties and glycidyl phenyl ether ( 2 ) was catalyzed by bis(p‐methoxybenzylidene)‐1,2‐diiminoethane/zinc chloride complex (ZnCl₂/ 3 ) at 30–150 °C for 6 h. No reaction of P1 and 2 took place below 70 °C, and it smoothly proceeded above 120 °C. The latencies and activities mean that ZnCl₂/ 3 meets both the high latencies at ambient conditions and the high activities at desired temperatures. Thermal crosslinking reaction employing multifunctional derivatives was carried out using ZnCl₂/ 3 at 140 °C for 6 h to afford a networked polymer in high yields. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3682–3689, 2008     

Penultimate effect in radical copolymerization of 2‐trifluoromethylacrylates

Electron‐deficient 2‐trifluoromethylacrylates (TFMA) undergo radical copolymerization with electron‐rich norbornene derivatives, vinyl ethers, and styrene derivatives, which can be described by the penultimate model much better than by the commonly employed terminal model. In an attempt to directly observe the effect of the CF₃ group in the penultimate unit on the radical reactivity, we employed the Giese's mercury method. 4,4,4‐Trifluorobutyl and n‐butyl radicals produced from respective alkylmercuric chlorides were competitively reacted with t‐butyl 2‐trifluoromethylacrylate (TBTFMA) and t‐butyl methacrylate (TBMA) and the products analyzed with gas chromatography. While TBTFMA has been found to be about 24times more reactive than TBMA toward the n‐butyl radical, the former is about 12 times more reactive than the latter toward the 4,4,4‐trifluorobutyl radical. Thus, the reactivity of the propagating radical toward TBTFMA in comparison with TBMA is suppressed by a factor of two when the penultimate unit has the CF₃ group. We observed a sextet electron spin resonance of the TFMA propagating radical with a coupling constant of ca. 25 gauss between the β‐proton and β‐fluorine. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1559–1565, 2008     

Synthesis and characterization of new complexes of the type [Ru(CO)2Cl2 (2‐phenyl‐1,8‐naphthyridine‐kN) (2‐phenyl‐1,8‐naphthyridine‐kN′)]. Preliminary applications in homogeneous catalysis

Novel ruthenium (II) complexes were prepared containing 2‐phenyl‐1,8‐naphthyridine derivatives. The coordination modes of these ligands were modified by addition of coordinating solvents such as water into the ethanolic reaction media. Under these conditions 1,8‐naphthyridine (napy) moieties act as monodentade ligands forming unusual [Ru(CO)₂Cl₂(η¹‐2‐phenyl‐1,8‐naphthyridine‐ kN )(η¹‐2‐phenyl‐1,8‐naphthyridine‐kN′)] complexes. The reaction was reproducible when different 2‐phenyl‐1,8‐naphthyridine derivatives were used. On the other hand, when dry ethanol was used as the solvent we obtained complexes with napy moieties acting as a chelating ligand. The structures proposed for these complexes were supported by NMR spectra, and the presence of two ligands in the [Ru(CO)₂Cl₂(η¹‐2‐phenyl‐1,8‐naphthyridine‐ kN )(η¹‐2‐phenyl‐1,8‐naphthyridine‐kN′)] type complexes was confirmed using elemental analysis. All complexes were tested as catalysts in the hydroformylation of styrene showing moderate activity in N,N′‐dimethylformamide. Copyright © 2008 John Wiley & Sons, Ltd.     

Highly stereo‐efficient synthesis and luminescence properties of novel trans‐regular vinylene– silylene–thiophene polymers

The novel trans‐stereo‐regular silylene–thiophene derivatives ( 4 , 5 ) with perfect consecutive silylene–arylene–silylene–vinylene linkage were synthesized via silylative coupling polycondensation of 2,5‐bis(vinyldimethylsilyl)thiophene ( 2 ) or 5,5′‐bis(vinyldimethylsilyl)‐2,2′‐bithiophene ( 3 ) catalyzed by ruthenium‐hydride complex [RuHCl(CO)(PCy₃)₂] ( 1 ). Their spectroscopic, absorption, and luminescence properties were characterized and compared with those of model compounds containing thiophene or bithiophene chromophores. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 127–137, 2008     

Electro‐optical behavior of ferroelectric liquid crystalline polyphenylene derivatives

Liquid crystalline (LC) polyphenylene derivatives, such as poly(para‐phenylene) (PPP), poly(meta‐phenylene) (PMP), poly(meta‐biphenylene) (PBP), and poly (meta‐terphenylene) (PTP) derivatives, were synthesized through substitution of fluorine‐containing chiral LC groups into side chains, with an aim to develop ferroelectric LC (FLC) conjugated polymers. All the polymers, except PTP, showed enantiotropic liquid crystallinities, where several types of mesophases were observed in both heating and cooling processes. Among them, PPP and PMP derivatives showed chiral smectic C (S_C*) phases responsible for ferroelectricity. In fact, they exhibited quick response to electric field, in spite of high viscosities inherent to polymers, giving rise to switching times of less than 1 s between two S_C states with reversely directed alignment. Hysteresis loops between the polarization and electric field were also observed for PPP and PMP. The spontaneous polarization (P_S) of PMP remained unchanged even after the electric field became zero, affording the residual polarization (P_R) whose value was the same as that of P_S. This indicates that PMP has a prospective memory function based on FLC nature. The present study is the first report for realizing a quick switching in macroscopic alignment using electric field and also for generating a potential memory function in π‐conjugated polymers. It is elucidated that unusual polymer main chains such as polyphenylenes can be used to prepare new ferroelectric polymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3591–3610, 2008     

A convenient synthesis of novel 7‐phosphonylbenzyl‐2‐substituted pyrazolo[4,3‐e]‐1,2,4‐triazolo[1,5‐c]‐pyrimidine derivatives

A series of pyrazolo[4,3‐e]‐1,2,4‐triazolo‐[1,5‐c]pyrimidine derivatives, bearing phosphonylbenzyl chain in position 7, were conveniently synthesized in an attempt to obtain potent and selective antagonists for the A_2A adenosine receptor or potent pesticide lead compounds. Diethyl[(5‐amino‐4‐cyano‐3‐methylsulfanyl‐pyrazol‐1‐yl)‐benzyl]phospho‐nate ( 3 ), which was prepared by the cyclization of diethyl 1‐hydrazinobenzylphosphonate ( 1 ) with 2‐[bis(methylthio)methylene]malononitrile ( 2 ), reacted with triethyl orthoformate to afford diethyl[(4‐cyano‐5‐ethoxymethyleneamino‐3‐methylsulfanyl‐pyrazol‐1‐yl)‐benzyl]phosphonate ( 4 ), which reacted with various acyl hydrazines in refluxing 2‐methoxyethanol to give the target compounds 5a–h in good yields. Their structures were confirmed by IR, ¹H NMR, ¹³C NMR, MS, and elemental analysis. The crystal structure of 5e was determined by single crystal X‐ray diffraction © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:634–638, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20478     

Rh‐ and Pt‐catalyzed cycloisomerization of enynes derived from terpenes

The Rh‐catalyzed cycloisomerization of new terpenoid derivatives featuring an O‐tethered enyne unexpectedly leads to polycyclic derivatives containing an inner cyclopropane ring or a diene moiety, depending on the structure of the enyne, as observed in the PtCl₂‐catalyzed processes. Copyright © 2008 John Wiley & Sons, Ltd.     

On the reaction of bis(phosphothioyl)disul‐fanes with hydroxamic acids,part I: Ionic versus radical reaction pathways

Among sodium N‐alkyl‐4‐chlorobenzo‐hydroxamates treated with bis(phosphothioyl)disul‐fanes >P(S)SSP(S)< (where >P(S) is phosphorothioyl, phosphonothioyl, and phosphinothioyl), only the N‐methyl one yields quantitatively the respective O‐phosphothioyl derivatives exhibiting complete inversion of configuration at phosphorus in a reaction whose products are inert toward dithiophosphate arising in the reaction. For branched N‐alkyl benzohydroxamates, products of a SET process predominated. The mechanism of the title reaction is discussed. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:271–282, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20423     

Theoretical studies on QSAR and mechanism of 2‐indolinone derivatives as tubulin inhibitors

The theoretical studies on three‐dimensional quantitative structure activity relationship (3D‐QSAR) and action mechanism of a series of 2‐indolinone derivatives as tubulin inhibitors against human breast cancer cell line MDA‐MB‐231 have been carried out. The established 3D‐QSAR model from the comparative molecular field analysis (CoMFA) shows not only significant statistical quality but also predictive ability, with high correlation coefficient (R² = 0.986) and cross‐validation coefficient (q² = 0.683). In particular, the appropriate binding orientations and conformations of these 2‐indolinone derivatives interacting with tubulin are located by docking study, and it is very interesting to find that the plot of the energy scores of these compounds in DOCK versus the corresponding experimental pIC₅₀ values exhibits a considerable linear correlation. Therefore, the inhibition mechanism that 2‐indolinone derivatives were regarded as tubulin inhibitors can be theoretically confirmed. Based on such an inhibition mechanism along with 3D‐QSAR results, some important factors improving the activities of these compounds were discussed in detail. These factors can be summarized as follows: the H atom adopted as substituent R₁, the substituent R₂ with higher electropositivity and smaller bulk, the substituents R₄–R₆ (on the phenyl ring) with higher electropositivity and larger bulk, and so on. These results can offer useful theoretical references for understanding the action mechanism, designing more potent inhibitors, and predicting their activities prior to synthesis. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

A facile synthesis of new 1,2‐dihydro‐2λ5‐[1,3]oxazolo[5,4‐d][1,3,2]diazaphosphinine derivatives starting from 2‐benzoylamino‐3, 3‐dichloroacrylonitrile

Easily accessible 2‐benzoylamino‐3,3‐dichloroacrylonitrile, when treated successively with primary amines, phosphorus pentachloride, sulfur dioxide, and various N‐ or S‐nucleophiles, furnishes the corresponding derivatives of 1,2‐dihydro‐2λ⁵‐[1,3]oxazolo[5,4‐d][1,3,2]diazaphosphinine, a novel fused heterocycle. The structure of the compounds obtained is unequivocally confirmed by spectroscopic methods and X‐ray diffraction analysis. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:506–511, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20470     

Palladaphosphacyclobutenes as catalysts in Heck and Suzuki reactions

Heck reactions of aryl halides with various olefins and Suzuki reactions of aryl halides with phenylboronic acid catalyzed by palladaphosphacyclobutene have been investigated. The scope of the Heck reaction has been investigated in N,N‐dimethylacetamide at 140 °C using NaOAc as base. Using 0.1% molar ratio of palladaphosphacyclobuyenes, aryl bromides were converted into 1,2‐substitutedethene products in good to high yields through coupling with both vinylarenes and acrylates. Actived aryl chloride reacted with styrene to afford 1,2‐substitutedethene products in moderate yields. The scope of the Suzuki reaction has been conducted in toluene at 110 °C using Cs₂CO₃ as base. Using 0.1% molar ratio of palladaphosphacyclobutene, aryl bromides reacted with phenylboronic acid to afford diaryl derivatives in excellent yield. Copyright © 2008 John Wiley & Sons, Ltd.     

Tris[tri(2‐thienyl)phosphine]palladium as the catalyst precursor for thiophene‐based Suzuki‐Miyaura crosscoupling and polycondensation

Zero‐valent palladium complex, Pd(PTh₃)₃, with three tri(2‐thienyl)phosphine ligands was prepared and characterized. Pd(PTh₃)₃ is superior to Pd(PPh₃)₄ in catalyzing Suzuki‐Miyaura coupling and polymerization of thiophene‐based derivatives. The Suzuki polycondensation of 3‐hexyl‐5‐iodothiophene‐2‐boronic pinacol ester with Pd(PTh₃)₃ as the catalyst precursor afforded high‐molecular‐weight P3HT with high regularity and yield. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4556–4563, 2008     

Synthesis,characterization, and fluorescence phenomena of 1‐naphthoxy and 1‐naphthylamino substituted cyclotriphosphazenes

The reactions of hexachlorocyclotriphosphazene N₃P₃Cl₆ ( 1 ) with 1‐naphthol and 1‐naphthylamine have been examined. The reaction of 1 with sodium 1‐naphthoxy gave the hexakis(1‐naphthoxy)cyclotriphosphazene ( 2 ) in high yield. Geminal 2,2‐di(1‐naphthylamino)‐4,4,6,6‐tetrachlorocyclotriphosphazene ( 3 ) was obtained from the reaction of 1 with 1‐naphthylamine. The structures of phosphazene derivatives were defined by elemental analysis, FTIR, UV‐‐visible, and ¹H, ¹³C, ³¹P NMR spectroscopy. The fluorescence intensity of the compounds was measured in THF and CH₂Cl₂. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:158–162, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20400     

Synthesis,structure, and biological activity of novel 4,5‐disubstituted thiazolyl urea derivatives

Novel 1‐(2,4‐dichlorophenyl)‐3‐[4‐aryl‐5‐(1H‐1,2,4‐triazol‐1‐yl)thiazol‐2‐yl] urea derivatives were synthesized by the reaction of 2‐amino‐4‐sustituted phentyl‐5‐(1H‐1,2,4‐triazol‐1‐yl) thiazoles with 2,4‐dichloro‐1‐isocyanatobenzene. Structures of the title compounds were confirmed by the elemental analysis, ¹H NMR, and single crystal X‐ray diffraction analysis. Biological evaluation showed that some of them possess promising antitumor activities. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:2–6, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20375     

Palladium N‐heterocyclic‐carbene‐catalyzed ortho‐arylation of benzaldehyde derivatives

New, sterically demanding 1,3‐dialkylbenzimidazolium salts ( 2a–c ) as N‐heterocyclic‐carbene precursors have been synthesized and characterized. The ortho position of aromatic aldehydes was directly and selectively arylated with aryl chlorides in the presence of a catalytic system prepared in situ from Pd(OAc)₂, 1,3‐dialkylbenzimidazolium chlorides ( 2a–c ), and Cs₂CO₃. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:569–574, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20479     

Synthesis,characterization, and nucleotidic chain cleavage ability of uncharged water soluble poly(ethylene glycol)‐fullerene derivatives with an amphiphilic character

Water‐soluble fullerenes containing two poly(ethylene glycol) branches [Full‐(PEG)₂] were prepared starting from commercial poly(ethylene glycol)‐monomethyl ethers and C₆₀ [Full‐(PEG)₂]s chemical characterization was made by FT‐IR, NMR, and MALDI‐TOF mass spectrometric analyses. Their thermal stability was determined by TGA experiments. The capability of C₆₀‐derivatives to induce oligonucleotide cleavage under visible light irradiation was also ascertained. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2154–2153, 2008     

Ruthenium‐catalyzed carbonylative cycloaddition reactions involving carbonyl and imino groups as assembling units

This paper describes carbonylative cycloaddition reactions catalyzed by Ru₃(CO)₁₂. Ru₃(CO)₁₂ was found to catalyze an intramolecular Pauson–Khand‐type reaction. Carbonylative cycloaddition reactions involving a carbonyl group in aldehydes, ketones, and esters as a two‐atom assembling unit were also achieved in the presence of Ru₃(CO)₁₂ as the catalyst. The reaction of 5‐hexyn‐1‐al and 6‐heptyn‐1‐al derivatives with CO in the presence of Ru₃(CO)₁₂ resulted in cyclocarbonylation from which bicyclic α, β‐unsaturated lactones were obtained. Intermolecular [2 + 2 + 1] carbonylative cycloaddition of alkenes, ketones, and CO was also catalyzed by Ru₃(CO)₁₂ as the catalyst to give saturated γ‐lactone derivatives. Simple ketones were not applicable, but ketones having a C?O or C?N group at the α‐position served as a good substrate. These reactions could be extended to carbonylative cycloaddition of the corresponding imines leading to γ‐butyrolactam derivatives. The [4 + 1] carbonylative addition of α,β‐unsaturated imines leading to unsaturated γ‐lactams was achieved with Ru₃(CO)₁₂. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 201–212; 2008: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20149