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Abstract: 5-Bromomethyl-4-nitroimidazoles have utility as bioreductive trigger precursors for the preparation of hypoxia-selective prodrugs. Here we describe an efficient two-step synthesis of 5-(bromomethyl)-1-methyl-4-nitro-1H-imidazole, a preferred precursor, employing an N-bromosuccinimide mediated radical bromination. Use of this precursor to prepare SN29966, a promising hypoxia-selective irreversible pan-ErbB inhibitor is reported along with the preparation of four other prodrug candidates. 5-Bromomethyl-4-nitroimidazole analogues bearing electron-donating and electron-withdrawing substituents at the N-1 and C-2 positions are also described. [Copyright &y& Elsevier]

Purpose: To evaluate the impact of intercellular adhesion molecule 1 (ICAM-1) in hyaluronic acid (HA) therapy in rats model of severe non-bacterial cystitis. Methods: Cystitis models in Sprague-Dawley female rats were produced by combination of intraperitoneal cyclophosphamide (CYP) with intravesical protamine/lipopolysaccharide (PS/LPS). HA or heparin (0.5 ml) was introduced intravesically to rats' bladders followed PS/LPS. Bladder tissue was prepared for histology including mast cell presence and measurement of ICAM-1, tumor necrosis factor (TNF)-α, and interleukin 6 (IL-6). Results: Cystitis model using intraperitoneal CYP and intravesical SP/LPS showed serious inflammation, higher mast cell count with elevated ICAM-1, TNF-α, and IL-6 levels. After intravesical heparin or HA treatment, incidence of grades 3-4 bladder inflammation and tissue ICAM-1 level were only significantly lower in HA group ( P = 0.017, P = 0.021, respectively), but not in heparin group ( P = 0.12, P = 0.798, respectively). Remarkably lower level of TNF-α ( P = 0.003) and ICAM-1 ( P = 0.006) was detected in HA-treated rats compared with heparin-treated rats. Inflammation grade and ICAM-1 level had strong correlation ( P < 0.001). IL-6 level after HA or heparin instillation had no difference. Conclusions: Intravesical administration of HA decreased the severity of bladder inflammation, mast cell presence, and levels of ICAM-1 and TNF-α in a rat model of severe non-bacterial cystitis; its effect was more obvious than that of heparin. Reduction of ICAM-1 may play a role in the anti-inflammatory effect of HA. [ABSTRACT FROM AUTHOR]

We report the synthesis of some heterobimetallic carbonyl clusters of groups 8 and 9 derived from diethynylsilane and diethynyldisilane ligands. The triosmium carbonyl clusters containing a pendant acetylene unit [(μ-CO)Os(CO)(μ-η-HC≡C-E-C≡CH)] [E = Si(CH), Si(CH)-Si(CH) and SiPh] were prepared and subsequently used for mixed-metal cluster formation. New diyne complexes of the type [{(μ-CO)Os(CO)}{Co(CO)}(μ-η:η-diyne)] and [{(μ-CO)Os(CO)}{(μ-H)Ru(CO)}(μ-η:μ-η, η-diyne)] [diyne = HC≡CSi(CH)C≡CH, HC≡CSi(CH)-Si(CH)C≡CH or HC≡CSi(Ph)C≡CH] have been prepared in good yields from the reaction of [(μ-CO)Os(CO)(μ-η-HC≡C-E-C≡CH)] with a molar equivalent of [Co(CO)] and [Ru(CO)], respectively. All the new heterobimetallic compounds have been characterized by IR and H NMR spectroscopy and mass spectrometry. The X-ray crystal structures and computational analyses based on density functional theory of these three molecules have been studied. Structurally, the dicobalt species adopts a pseudo-tetrahedral CoC core with the alkyne bond which lies essentially perpendicular to the Co-Co vector. For the mixed osmium-ruthenium analogue, the hexanuclear carbonyl cluster consist of two trinuclear metal cores with the μ-(η-||) bonding mode for the acetylene group in the former case and the μ-η, η bonding mode in the latter one. [ABSTRACT FROM AUTHOR]

Study Type - Therapy (RCT) Level of Evidence 1b What's known on the subject? and What does the study add? Hemorrhagic cystitis (HC) is a relatively rare bladder disease with a complex etiology. With the growing number of patients with pelvic radiation therapy, incidence of this disease has risen considerably. Although treatments like hyperbaric oxygen (HBO) had some benefit to improve the symptoms, the optimal treatment of this disease still remains a tough problem. We reported our experience of intravesical hyaluronic acid (HA) and HBO in treating HC and the results seemed interesting. Intravesical HA is easier to do and well tolerated, and it showed a sustained decrease of bladder bleeding, pelvic pain and frequency of voiding for at least 12 months. We suggest it as an alternative and potential way in treating HC. OBJECTIVE [ABSTRACT FROM AUTHOR]

Abstract: A series of cobalt complexes of the potent DNA minor groove alkylator 1-(chloromethyl)-3-(5,6,7-trimethoxyindol-2-ylcarbonyl)-2,3-dihydro-1H-pyrrolo[3,2-f]quinolin-5-ol (seco-6-azaCBI-TMI) were prepared from a series of N-substituted cyclen ligands. The final N-substituted complexes carried formal overall charges ranging from +2 to −2 and showed limited improvements in solubility. They showed similar stabilities to that of the complex with the unsubstituted cyclen ligand, and large but variable attenuation of the cytotoxicity of the free alkylator (2–30-fold), compared to 150-fold for the unsubstituted ligand. However, they had oxic/hypoxic ratios (2–22-fold) comparable to that of the unsubstituted cyclen complex (5). [Copyright &y& Elsevier]

Drug resistant tuberculsosis (TB) is global health crisis that demands novel treatment strategies. Bacterial ATP synthase inhibitors such as bedaquiline and next-generation analogues (such as TBAJ-876) have shown promising efficacy in patient populations and preclinical studies, respectively, suggesting that selective targeting of this enzyme presents a validated therapeutic strategy for the treatment of TB. In this work, we report tetrahydronaphthalene amides (THNAs) as a new class of ATP synthase inhibitors that are effective in preventing the growth of Mycobacterium tuberculosis (M.tb) in culture. Design, synthesis and comprehensive structure-activity relationship studies for approximately 80 THNA analogues are described, with a small selection of compounds exhibiting potent (in some cases MIC 90 <1 μg/mL) in vitro M.tb growth inhibition taken forward to pharmacokinetic and off-target profiling studies. Ultimately, we show that some of these THNAs possess reduced lipophilic properties, decreased hERG liability, faster mouse/human liver microsomal clearance rates and shorter plasma half-lives compared with bedaquiline, potentially addressing of the main concerns of persistence and phospholipidosis associated with bedaquiline. [Display omitted] • Tetrahydronaphthalene amides are novel inhibitors of M.tb in culture. • Selective and potent inhibitors of the mycobacterial ATP synthase. • Improved hERG liability, clearance and half-life compared to bedaquiline. [ABSTRACT FROM AUTHOR]

[Display omitted] During our studies into preparing analogues of pyrazolopyrimidine as ATP synthesis inhibitors of Mycobacterium tuberculosis , a regiospecific condensation reaction between ethyl 4,4,4-trifluoroacetoacetate and 3-(4-fluorophenyl)-1 H -pyrazol-5-amine was observed which was dependent on the specific reaction conditions employed. This work identifies optimized reaction conditions to access either the pyrazolo[3,4- β ]pyridine or the pyrazolo[1,5- α ]pyrimidine scaffold. This has led to the structural confirmation of the previously reported pyrazolopyrimidine 17b which was reported as pyrazolo[1,5- α ]pyrimidine structure 2 which was corrected to pyrazolo[3,4- β ]-pyrimidine 19. [ABSTRACT FROM AUTHOR]

Abstract: Treatment of Os(κ2-S2CNMe2)H(CO)(PPh3)2 with HSiMeCl2 or HSiCl3 gives in high yield Os(κ2-S2CNMe2)(SiMeCl2)(CO)(PPh3)2 (1) or Os(κ2-S2CNMe2)(SiCl3)(CO)(PPh3)2 (2), respectively. The crystal structures of both compounds have been determined and the Os–Si distances are 2.3672(10)Å for 1 and 2.3449(12)Å for 2. In solution, and under forcing conditions, both compounds are extraordinarily unreactive towards hydroxide ions. [Copyright &y& Elsevier]

Abstract: Treatment of the six-coordinate trimethylstannyl complex, Os(SnMe3)(κ2-S2CNMe2)(CO)(PPh3)2 (1) with SnMe2Cl2 produces Os(SnMe2Cl)(κ2-S2CNMe2)(CO)(PPh3)2 (2), which in turn reacts readily with hydroxide ion to give, Os(SnMe2OH)(κ2-S2CNMe2)(CO)(PPh3)2 (3). The osmastannol complex 3 undergoes a reaction with 2 equivalents of t BuLi, in which one of the phenyl rings of a triphenylphosphine ligand is “ortho-stannylated”, without cleavage of the Os–Sn bond, to give the cyclic complex, Os(κ2(Sn,P)-SnMe2C6H4PPh2)(κ2-S2CNMe2)(CO)(PPh3) (4). This novel cyclic complex is selectively functionalised at the tin atom by reaction with SnMe2Cl2 which exchanges one methyl group for chloride giving the diastereomeric mixture, Os(κ2(Sn,P)-SnMeClC6H4PPh2)(κ2-S2CNMe2)(CO)(PPh3) (5a/5b). Crystal structure determination reveals that both diastereomers occur in the unit cell. The mixture, 5a/5b, undergoes reaction with hydroxide ion to give the diastereomeric osmastannol complexes, Os(κ2(Sn,P)-SnMeOHC6H4PPh2)(κ2-S2CNMe2)(CO)(PPh3) (6a/6b) and with sodium borohydride to give the corresponding tin-hydride mixture, Os(κ2(Sn,P)-SnMeHC6H4PPh2)(κ2-S2CNMe2)(CO)(PPh3) (7a/7b). Crystal structure determinations for 2, 4, and 5a/5b have been obtained. [Copyright &y& Elsevier]

Abstract: Heating the five-coordinate trimethylstannyl complex, Os(SnMe3)Cl(CO)(PPh3)2, in solution with triphenylphosphine induces an ortho-stannylation of one phenyl group of a triphenylphosphine ligand and an ortho-metallation of another triphenylphosphine ligand, to produce the metallacyclic complexes, Os(κ2(Sn,P)-SnMeClC6H4PPh2)(κ2(C,P)-C6H4PPh2)(CO)(PPh3) (1) and Os(κ2(Sn,P)-SnMe2C6H4PPh2)(κ2(C,P)-C6H4PPh2)(CO)(PPh3) (2), suggesting the possible intermediacy of a complex with a coordinated stannylene ligand. Spectroscopic data indicate that only one diastereomer of 1 is formed and crystal structure determination of 1 reveals that this is the diastereomer with chloride directed towards the CO ligand. Complex 2 is converted to 1 through a redistribution reaction with SnMe2Cl2. Heating the six-coordinate trimethylstannyl complex, Os(SnMe3)Cl(CO)2(PPh3)2, in solution produces the osmium(II) methyl complex, Os(Me)(SnMe2Cl)(CO)2(PPh3)2 (3), through an exchange of methyl and chloride groups on the tin and osmium. In this rearrangement, the relative locations of the two CO ligands and the two PPh3 ligands remains unchanged. However, when the six-coordinate trimethylstannyl complex, Os(SnMe3)Cl(CO)2(PPh3)2 is heated under CO, the same exchange reaction is observed but the mono-triphenylphosphine, tricarbonyl complex, Os(Me)(SnMe2Cl)(CO)3(PPh3) (4), is produced and here the SnMe2Cl ligand is located trans to the PPh3 ligand. Crystal structure determinations for 1, 2, 3, and 4 have been obtained. [Copyright &y& Elsevier]

Abstract: Reaction between Os(SiCl3)Cl(CO)(PPh3)2 and five equivalents of MeLi produces a colourless intermediate, tentatively formulated as the lithium salt of the six-coordinate, dimethyl, trimethylsilyl-containing complex anion, Li[Os(SiMe3)(Me)2(CO)(PPh3)2]. Reaction of this material with ethanol releases methane and gives the red, coordinatively unsaturated methyl, trimethylsilyl-containing complex, Os(SiMe3)(Me)(CO)(PPh3)2 (1). An alternative synthesis of 1 is to add one equivalent of MeLi to Os(SiMe3)Cl(CO)(PPh3)2, which in turn is obtained by adding three equivalents of MeLi to Os(SiCl3)Cl(CO)(PPh3)2. Treatment of 1 with p-tolyl lithium, again gives a colourless intermediate which may be Li[Os(SiMe3)(Me)(p-tolyl)(CO)(PPh3)2], and reaction with ethanol gives the red complex, Os(SiMe3)(p-tolyl)(CO)(PPh3)2 (3). Complexes 1 and 3 are readily carbonylated to Os(SiMe3)(Me)(CO)2(PPh3)2 (2) and Os(SiMe3)(p-tolyl)(CO)2(PPh3)2 (4), respectively. Heating Os(SiMe3)Cl(CO)(PPh3)2 in molten triphenylphosphine results only in loss of the trimethylsilyl ligand and formation of the previously known complex containing an ortho-metallated triphenylphosphine ligand, Os(κ2(C,P)-C6H4PPh2)Cl(CO)(PPh3)2. In contrast, heating the five-coordinate osmium-methyl complex, Os(SiMe3)(Me)(CO)(PPh3)2 (1), in the presence of triphenylphosphine results mainly, not in tetramethylsilane elimination, but in ortho-silylation as well as ortho-metallation of different triphenylphosphine ligands giving, Os(κ2(Si,P)-SiMe2C6H4PPh2)(κ2(C,P)-C6H4PPh2)(CO)(PPh3) (5). A byproduct of this reaction is the non-silicon containing di-ortho-metallated complex, Os(κ2(C,P)-C6H4PPh2)2(CO)(PPh3) (6). A similar reaction occurs when Os(SiMe3)(Me)(CO)(PPh3)2 (1) is heated in the presence of tri(N-pyrrolyl)phosphine producing Os(κ2(Si,P)-SiMe2C6H4PPh2)(κ2(C,P)-C6H4PPh2)(CO)[P(NC4H4)3] (7) but a better synthesis of 7 is to treat 5 directly with tri(N-pyrrolyl)phosphine. Heating the six-coordinate complex, Os(SiMe3)(Me)(CO)2(PPh3)2 (2), gives two complexes both containing ortho-metallated triphenylphosphine, one with loss of the trimethylsilyl ligand, giving the known complex, Os(κ2(C,P)-C6H4PPh2)H(CO)2(PPh3), and the other with retention of the trimethylsilyl ligand, giving Os(SiMe3)(κ2(C,P)-C6H4PPh2)(CO)2(PPh3) (8). Crystal structure determinations for 5, 6, 7 and 8 have been obtained. [Copyright &y& Elsevier]

Reaction of the platinum bis(alkynyl) complex [Pt(dppf)(C&z.tbnd6;CPh)2] (1) (dppf=bis(diphenylphosphino)ferrocene) with an equimolar amount of Group 11 metal salts [Cu(NCMe)4]BF4 and AgBF4 initially gives 1:1 mixed-metal complexes [Pt(dppf)(C&z.tbnd6;CPh)2Cu(NCMe)]BF4 (2) and [Pt(dppf)(C&z.tbnd6;CPh)2Ag]BF4 (3) in good yields. Upon standing in solution at room temperature, compounds 2 and 3 rearrange and aggregate to the corresponding diplatinum complexes [{Pt(dppf)(C&z.tbnd6;CPh)2}2M]BF4 (M=Cu (4), Ag (5)) which exhibit an intense molecular ion envelope for the respective cation in their electrospray mass spectra. Compounds 4 and 5 can also be formed when the reaction is performed using a 2:1 molar ratio of 1 and the Group 11 salts. The X-ray crystal structures of 1, 4 and 5 have been determined. Structures of 4 and 5 reveal that the two square-planar platinum coordination planes in the cation are approximately orthogonal and the Group 11 metal ion is bonded in an η2-fashion to four carbon&z.sbnd;carbon triple bonds to afford heterometallic pentanuclear Fe2Pt2M complexes (M=Cu, Ag) in which each platinum center is stabilized by a dppf ligand. Each of the new complexes displays a reversible oxidation couple corresponding to the ferrocenyl unit of dppf and there is less stabilization of the silver in the mixed-metal complex than in the copper congeners. [Copyright &y& Elsevier]

Pyrazolo[1,5-a]pyrimidines have been reported as potent inhibitors of mycobacterial ATP synthase for the treatment of Mycobacterium tuberculosis (M.tb). In this work, we report the design and synthesis of approximately 70 novel 3,5-diphenyl-N-(pyridin-2-ylmethyl)pyrazolo[1,5-a]pyrimidin-7-amines and their comprehensive structure–activity relationship studies. The most effective pyrazolo[1,5-a]pyrimidin-7-amine analogues contained a 3-(4-fluoro)phenyl group, together with a variety of 5-alkyl, 5-aryl and 5-heteroaryl substituents. A range of substituted 7-(2-pyridylmethylamine) derivatives were also active. Some of these compounds exhibited potent in vitro M.tb growth inhibition, low hERG liability and good mouse/human liver microsomal stabilities, highlighting their potential as inhibitors of M.tb. [ABSTRACT FROM AUTHOR]

A series of 5,8-disubstituted tetrahydroisoquinolines were shown to be effective inhibitors of M. tb in culture and modest inhibitors of M. tb ATP synthase. There was a broad general trend of improved potency with higher lipophilicity. Large substituents (e.g., Bn) at the tetrahydroquinoline 5-position were well-tolerated, while N -methylpiperazine was the preferred 8-substituent. Structure-activity relationships for 7-linked side chains showed that the nature of the 7-linking group was important; –CO– and –COCH 2 – linkers were less effective than –CH 2 – or –CONH– ones. This suggests that the positioning of a terminal aromatic ring is important for target binding. Selected compounds showed much faster rates of microsomal clearance than did the clinical ATP synthase inhibitor bedaquiline, and modest inhibition of mycobacterial ATP synthase. [ABSTRACT FROM AUTHOR]

The treatment of 2-(ArNC(H))C6H4-HNC9H6N with n-BuLi and the subsequent addition of CuCl2 afforded the anilido-aldimine Cu(II) complexes 1-5 Cu[{2-[ArN=C(H)]C6H4}N(8-C9H6N)]Cl (Ar = 2,6-iPr2C6H3 (1), 2,4,6-(CH3)3C6H2 (2), 4-OCH3C6H4 (3), 4-BrC6H4 (4), 4-ClC6H4 (5)), respectively. All the copper complexes were fully characterized by IR, EPR and HR-MS spectra. The X-ray diffraction analysis reveals that 2 and 4 are mononuclear complexes, and the Cu atom is sitting in a slightly square-planar geometry. These Cu(II) complexes have exhibited excellent catalytic activity in the Chan–Lam coupling reactions of benzimidazole derivatives with arylboronic acids, achieving the highest yields of up to 96%. [ABSTRACT FROM AUTHOR]

Background: Previous studies on dynamic impingement of nerve root in cervical spondylotic radiculopathy (CSR) have focused on effect of cervical spine motion (CSM) on dimensional changes of intervertebral foramen. However, there are few studies to investigate effect of CSM on displacement of posterolateral intervertebral disc until now. The present study aimed to investigate effect of CSM on displacement of posterolateral annulus fibrosus (AF) in CSR with contained posterolateral disc herniation. Methods: A C5–C6 CSR finite element model with unilateral contained posterolateral disc herniation was generated based on validated C5–C6 normal finite element model. Forward and backward displacement distributions of posterolateral AFs in CSR model and normal model were compared. Changes in forward and backward displacement magnitudes of posterolateral AFs of the herniated side and the healthy side in CSR model, with respect to those of the ipsilateral posterolateral AFs in normal model, were compared. The comparisons were performed under flexion, extension, lateral bendings and axial rotations. Results: There was no difference in deformation trend of posterolateral AF between CSR model and normal model. Bilateral posterolateral AFs mainly moved forward during flexion and backward during extension. Left posterolateral AF mainly moved backward and right posterolateral AF forward during left lateral bending and left axial rotation. Left posterolateral AF mainly moved forward and right posterolateral AF backward during right lateral bending and right axial rotation. However, with respect to forward and backward displacement magnitudes of the ipsilateral posterolateral AFs in normal model, those of the herniated side increased relatively significantly compared with those of the healthy side in CSR model. Conclusions: Flexion, lateral bending to the healthy side and axial rotation to the healthy side make posterolateral AF of the herniated side mainly move forward, whereas extension, lateral bending to the herniated side and axial rotation to the herniated side make it mainly move backward. These data may help select CSM or positions to diagnose and treat CSR with contained posterolateral disc herniation. Increase in deformation amplitude of posterolateral AF of the herniated side may also be the reason for dynamic impingement of nerve root in CSR with contained posterolateral disc herniation. [ABSTRACT FROM AUTHOR]

Various synthetic methods leading to 5-(bromomethyl)-4-nitroimidazoles are described. [ABSTRACT FROM AUTHOR]

Reactions of Ru3(CO)12 with 6‐methyl‐2‐pyridinyl‐ethanol ligands 6‐CH3‐2‐PyCH2CR1R2OH [R1H, R22‐CH3OC6H4 (L1H); R1H, R22‐CF3C6H4 (L2H); R1R2CH3 (L3H); and R1H, R22,6‐(CH3O)2C6H3 (L4H)] in refluxing THF afforded the corresponding trinuclear ruthenium clusters (6‐CH3‐2‐PyCH2CR1R2O)(μ2‐H)Ru3(CO)9 [R1H, R22‐CH3OC6H4 (1); R1H, R22‐CF3C6H4 (2); R1R2CH3 (3); and R1H, R22,6‐(CH3O)2C6H3 (4)], respectively. All the four new clusters were well characterized by elemental analysis, IR, 1H, and 13C nuclear magnetic resonance. Furthermore, their crystal structures were determined by single‐crystal X‐ray diffraction analysis. The ruthenium clusters were proved to be efficient catalysts for the oxidation of saturated CH bonds with tert‐butyl hydroperoxide (TBHP) as the oxidant in CH3CN/H2O (1:4) at room temperature. [ABSTRACT FROM AUTHOR]

[Display omitted] l -Glutathione (GSH) has exceptional antioxidant activities against UVA irradiation-induced oxidative stress and is used widely for combatting skin ageing. However, topical administration of GSH is challenging due to its inability to penetrate the stratum corneum (SC). This study aims to evaluate the solid lipid nanoparticles (SLNs) carrier system for improving the skin penetration and stability of GSH. The GSH-loaded SLNs (GSH-SLNs) were prepared by the double emulsion technique and were optimized by a full factorial design. The optimized GSH-SLNs formulation had a mean particle size of 305 ± 0.6 nm and a zeta potential of + 20.1 ± 9.5 mV, suitable for topical delivery. The ex-vivo penetration study using human skin demonstrated a 3.7-fold improvement of GSH penetration across SC with GSH-SLNs when compared with aqueous GSH. GSH-SLNs prolonged antioxidant activity on UVA irradiated fibroblast cells when compared to GSH solution, preventing UVA-induced cell death and promoting cell growth for times over 48 h. This research has illustrated that as a carrier system, SLNs were able to enhance the physicochemical stability, skin penetration, and drug deposition in the viable epidermis and dermis layers of the skin for GSH, while also maintaining the ability to protect human skin fibroblast cells against oxidative stress caused by UVA irradiation. This delivery system shows future promise as a topical delivery platform for the topical delivery of GSH and other chemically similar bioactive compounds for improving skin health. [ABSTRACT FROM AUTHOR]

A Pd-catalysed amination method is used to convert seco -CBI, a synthetic analogue of the alkylating subunit of the duocarmycin natural products, from the phenol to amino form. This allows efficient enantioselective access to the more potent S enantiomer of aminoCBI and its incorporation into analogues of DNA minor groove cross-linking agents. Evaluation in a panel of nine human tumour cell lines shows that the bifunctional agents containing aminoCBI are generally less cytotoxic than their phenolCBI analogues and more susceptible to P-glycoprotein-mediated resistance. However, all bifunctional agents are potent cytotoxins, some in the sub-pM IC 50 range, with in vitro properties that compare favourably with established microtubule-targeted ADC payloads. [ABSTRACT FROM AUTHOR]

Objective: To compare the results of ureteroscopic lithotripsy (URSL) with retroperitoneal laparoscopic ureterolithotomy (RPLU) as two minimally invasive techniques in the management of proximal ureteral stones larger than 12 mm. Patients and methods: From January 2009 to October 2013, patients with impacted unilateral upper ureteral stones larger than 12 mm were enrolled including 182 males and 93 females with a medium age of 40 years (22-72 years). Patients were randomized to receive URSL (139 cases) with semirigid ureteroscope or RPLU (136 cases). Results: Stone size was similar in RPLU and URSL groups (13.8 ± 1.9 vs 13.6 ± 1.4 mm, P = 0.312). Operating time and hospitalizing days in URSL group were significantly shorter than those in RPLU group ( P < 0.001), whereas stone clearance rate was significantly higher in RPLU group (97.1 vs 89.9 %, P = 0.017). Ureteral strictures happened higher in URSL group (5 patients, 3.6 %) than RPLU group (2 patients, 1.5 %) with no statistical significance, while the strictures requiring surgical intervention were significantly higher in URSL group (4 cases) (2.9 vs 0 %, P = 0.046). Conclusion: RPLU could provide better stone clearance rate than semirigid URSL for upper ureteral impacted stones larger than 12 mm. It may also reduce the chance of surgical intervention for postoperative ureteral stricture. [ABSTRACT FROM AUTHOR]

• Ru(II) Schiff-base complexes showed high activity in acceptorless dehydrogenative reaction. • The primary alcohols were selectively oxidized to give the corresponding aldehydes. • The secondary alcohols were smoothly to afford the ketones in good to excellent yields. • The present catalytic system displayed wide substrate scope and operated under mild conditions. The catalytic performance of ruthenium carbonyl complexes containing Schiff base ligands [RN CH(C 10 H 6 O)] 2 Ru(CO) 2 [R = C 6 H 5 (1); 4-CH 3 C 6 H 4 (2) ; 4-OCH 3 C 6 H 4 (3); R = 2,6-(CH 3) 2 C 6 H 3 (4); 4-ClC 6 H 4 (5); 4-BrC 6 H 4 (6); 4-CF 3 C 6 H 4 (7)] were explored in acceptorless dehydrogenative oxidation of alcohols with the releasing of hydrogen as the only by-product. All the Ru complexes 1–7 demonstrated good catalytic activities in oxidation of secondary alcohols to furnish the corresponding ketone products in excellent yields. Moreover, these Ru complexes displayed good selectivity in oxidation of primary alcohols to affording the aldehydes as the final products in 37–96 % yields. Among the complexes, the complex 7 , which having an electron-withdrawing group (-CF 3) showed the best catalytic activity. A series of schiff base supported ruthenium(II) complexes were found to be efficient catalysts in acceptorless dehydrogenative oxidation of both primary and secondary alcohols to give the corresponding ketones and aldehydes, respectively, in moderate to excellent yields. [Display omitted] [ABSTRACT FROM AUTHOR]

Treatment of Ru3(CO)12 with one equivalent of 2‐indolyl‐6‐pyridinyl‐alcohol ligands 2‐(C8H6N)‐6‐(CR1R2OH)C5H3N (R1 = R2 = Me (L1H); R1 = R2 = C2H5 (L2H); R1, R2 = −(CH2)4‐ (L3H);& R1, R2 = −(CH2)5‐ (L4H)) in refluxing THF afforded the corresponding trinuclear ruthenium clusters L(μ2‐H)Ru3(CO)9 (1a–1d), respectively. All the novel Ru complexes were well characterized by NMR, elemental analyses and IR spectra. Structures of complexes 1a, 1c, and 1d were further determined by X‐ray crystallographic studies. Complexes 1a–1d were applied to catalytic Oppenauer‐type oxidation of secondary alcohols with acetone as oxidant, and complex 1a was found to be the most efficient catalyst. [ABSTRACT FROM AUTHOR]

Abstract: Quaternary salt analogues based on the DNA minor groove binder and adenine N3 alkylating agent 5-amino-1-(chloromethyl)-1,2-dihydro-3H-benz[e]indole (aminoCBI) show remarkable effects on the body weight of mice (a long-term failure to gain weight relative to matched controls with no loss of appetite or perceptible deterioration in health) following administration of a single (non-toxic) dose between about 0.5–5μmol/kg. The nature of the quaternizing group was not important, but a related hydroxyCBI analogue was much less effective. Compounds where the chloro group was replaced by a hydrogen or hydroxy group (thus abrogating DNA alkylating capability) showed no weight control activity. It is speculated, based on other studies, that the marked long-term weight control effect is due to inhibition of bile flow into the intestine and reduced absorption of triglycerides, together with accelerated cell death in spleen and white adipose tissues due to drug accumulation there. This class of compound may serve as interesting tools for further study of these phenomena. [Copyright &y& Elsevier]

New ligands H2L2–H2L6 comprise the cyclen macrocycle which is N,N′-dialkylated at the 1,7-nitrogen atoms by three- and four-carbon alkyl chains bearing terminal sulfonic (C3H2L2), phosphonic (C3H2L3, C4H2L4) or carboxylic acid (C3H2L5, C4H2L6) groups, and HL7 is N-monoalkylated by a four-carbon sulfonic acid group. The ligands were prepared by alkylation of a bridged bisaminal intermediate. The syntheses of cobalt(iii) complexes containing a tetradentate cyclen, N,N′-1,7-Me2cyclen, cyclam or L2–L7 ligand together with the bidentate 8-quinolinato (8QO−) ligand, of interest as it is a model for a more potent cytotoxic analogue, were investigated. Coordination of ligands (L) cyclen, N,N′-1,7-Me2cyclen or cyclam to cobalt(iii) was achieved using Na3[Co(NO6)] to form [Co(L)(NO2)2]+. HOTf (trifluoromethansulfonic acid) was used to prepare the triflato complexes [Co(L)(OTf)2]+, followed by substitution of the labile triflato ligands to yield [Co(L)(8QO)](ClO4)2isolated as the perchlorate salts. One further example containing cyclam and the 5-hydroxymethyl-8-quinolinato ligand was also prepared by this method. Complexes containing the pendant arm ligands L2–L6 were prepared from the cobalt precursor trans-[Co(py)4Cl2]+. Reaction of this complex with H2L2·4HCl and 8QOH produced [Co(L2)(8QO)] in one step and contains two deprotonated sulfonato pendant arms. The reaction of H2L3·4HBr with [Co(py)4Cl2]+gave [Co(L3)]Cl in which L3 acts as a hexadenate ligand with the three-carbon phosphonato side chains coordinated to cobalt. H2L5·4HCl bearing three-carbon carboxylic acid pendant arms gave a similar result. The four-carbon ligands were coordinated to cobalt by reaction of [Co(py)4Cl2]+with H2L4·4HBr or H2L6·4HCl to give [Co(HL4)Cl2] or [Co(H2L6)Cl2]Cl, which in turn with 8QOH gave the 8QO−complexes [Co(L4)(8QO)] bearing anionic phosphate pendant arms or [Co(H2L6)(8QO)]Cl2containing neutral carboxylic acid side chains. The reaction of Na3[Co(CO3)3] with the mono-N-alkylated ligand HL7·4HCl and then HOTf gave [Co(L7)(CO3)] and then in turn [Co(L7)(OTf)2]. The carbonato complex [Co(L7)(CO3)] with [8QO]2[SO4] produced [Co(L7)(CO3)]. All complexes containing L7 bear an anionic sulfonato group on the side chain. The synthesis and characterisation of the six new ligands based on N-alkylated cylen ligand and the cobalt complexes outlined above are described, along with cyclic voltammograms of the 8QO−complexes and the molecular structures determined by X-ray crystallography of [Co(cyclen)(H2O)2](OTf)3(formed by aquation of the triflato complex), [Co(cyclen)(8QO)](ClO4)2, Co(L2)(8QO)·2H2O, Co(L4)(8QO)·6H2O and [Co(H2L6)Cl2]Cl·H2O. These demonstrate the coordination of the cyclen ligand in the folded anti-O,syn-Nconfiguration with the N-alkylated nitrogens occupying apical positions. [ABSTRACT FROM AUTHOR]

Abstract: Treatment of the five-coordinate chlorodimethylsilyl complex, Os(SiMe2Cl)Cl(CO)(PPh3)2 with hydroxide readily produces Os(SiMe2OH)Cl(CO)(PPh3)2 (1). Complex 1 is deprotonated by tBuLi giving the silanolate complex, Os(SiMe2OLi)Cl(CO)(PPh3)2 (2), which reacts further with Me3SiCl or Me3SnCl to give Os(SiMe2OSiMe3)Cl(CO)(PPh3)2 (3) or Os(SiMe2OSnMe3)Cl(CO)(PPh3)2 (4), respectively. The structures of 3 and 4 have been determined by X-ray crystallography. Reaction between OsH(κ2-S2CNMe2)(CO)(PPh3)2 and HSiMe2Cl gives Os(SiMe2Cl)(κ2-S2CNMe2)(CO)(PPh3)2 (5). This six-coordinate chlorodimethylsilyl complex, is unreactive towards hydroxide at room temperature and at 60 °C forms Os[Si(OH)3](κ2-S2CNMe2)(CO)(PPh3)2 (7). Complex 5 is, however, smoothly converted to the hydroxy derivative, Os(SiMe2OH)(κ2-S2CNMe2)(CO)(PPh3)2 (6) upon chromatography on silica gel. Complex 6 is deprotonated by tBuLi giving the intermediate silanolate complex, Os(SiMe2OLi)(κ2-S2CNMe2)(CO)(PPh3)2, which reacts further with Me3SiCl to give Os(SiMe2OSiMe3)(κ2-S2CNMe2) (CO)(PPh3)2 (8). Crystal structure determinations for 5, 6, 7, and 8 have been obtained and structural comparisons of these related compounds are made. [Copyright &y& Elsevier]

The use of the ligands, diethynyldiphenylsilane and 1,3-diethynyltetramethyldisiloxane, in the synthesis of Group 8 metal σ-acetylide mononuclear complexes is demonstrated. New complexes trans-[(dppm)2ClMC&z.tbnd6;CSi(Ph)2C&z.tbnd6;CH] (M=Ru 1; Os 2) and trans-[(dppm)2ClMC&z.tbnd6;CSi(Me)2–O–Si(Me)2C&z.tbnd6;CH] (M=Ru, 3; Os, 4) featuring different silyl units were prepared from a mixture of cis-[M(dppm)2Cl2] and HC&z.tbnd6;CSi(Ph)2C&z.tbnd6;CH or HC&z.tbnd6;CSi(Me)2–O–Si(Me)2C&z.tbnd6;CH in the presence of NaPF6 followed by deprotonation with 1,8-diazabicyclo[5.4.0]undec-7-ene. All the new complexes have been fully characterized by FTIR and NMR spectroscopies and fast atom bombardment mass spectrometry. Single-crystal X-ray structures of 1 and 2 confirm that the two diphosphines adopt a trans geometry at the metal centre and one of the terminal ethynyl groups remains intact. Complexes 1–4 show reversible redox chemistry and their half-wave potentials due to the metal centres are less anodic than those for the starting precursors cis-[M(dppm)2Cl2] (M=Ru, Os). [Copyright &y& Elsevier]

Four ruthenium(II) complexes 1—4 [RN=CH‐(2,4‐(tBu)2C6H2O)]RuH(PPh3)2(CO) (R = C6H5, 1; R = 4‐MeC6H4, 2; R = 4‐ClC6H4, 3; R = 4‐BrC6H4, 4) bearing Schiff base ligands were prepared by treating RuHClCO(PPh3)3 with RN=CH‐(2,4‐(tBu)2C6H2OH (L1—L4) in the presence of triethylamine. Their structures were fully characterized by elemental analysis, IR, NMR spectroscopy and X‐ray crystallography. These Ru(II) complexes exhibit high catalytic performance and good functional‐group compatibility in the acceptorless dehydrogenation of secondary alcohols, affording the corresponding ketones in 82%—94% yields. [ABSTRACT FROM AUTHOR]

Four trinuclear ruthenium carbonyl clusters, (6-BrPyCHRO)2Ru3(CO)8 (R = 4-OCH3C6H4, 1a; R = 4-BrC6H4, 1b) and (2-OC6H4–HC＝N–C6H4R)2Ru3(CO)8 (R = 4-OCH3, 2a; R = 4-Br, 2b), were synthesized from the reactions of Ru3(CO)12 with the corresponding N,O-bidentate ligands (two pyridyl alcohols and two Schiff bases) respectively in a ratio of 1 : 2. Three new complexes 1b, 2a and 2b have been fully characterized by elemental analysis, FT-IR, NMR and X-ray crystallography. The catalytic activity of these ruthenium complexes for the aerobic oxidation of primary benzylic amines to amides and nitriles in the presence of t-BuOK was investigated, of which the Schiff base complex 2a was found to exhibit the highest activity. [ABSTRACT FROM AUTHOR]

• A piconol ligand based cluster was synthesized and it is stable to air and moisture. • The Ru clusters were found to be efficient catalysts for C H oxidation of hydrocarbons with TBHP as the oxidant. • The catalytic system displayed good functional group compatibility and was carried out at room temperature. Trinuclear ruthenium clusters supported by piconol ligands [6-C 8 H 6 N-PyCR1R2O](μ 2 H)Ru 3 (CO) 9 (R1 = R2 = CH 3 (1); R1 = R2 = CH 2 CH 3 (2); R1, R2 = -(CH 2) 4 - (3); R1 = CH 3 , R2 = Ph (4)) have been proved to be efficient catalysts for the oxidation of saturated C H bonds. Cluster 1 was found to be the most active of the four, which can catalyze the oxidation of various hydrocarbons, with tert ‑butyl hydroperoxide as the oxidant in CH 3 CN/H 2 O at room temperature, to afford the corresponding ketones in excellent yields. [Display omitted] [ABSTRACT FROM AUTHOR]

• Cheap and readily available ligands, air- and moisture-stable catalysts. • Highly efficient for benzylic C-H oxidation. • Mild reaction conditions, broad substrate scope, environmentally benign methodology. Thermal reactions of Ru 3 (CO) 12 with two equivalents of N,O-bidentate ligands L1H - L7H (naphthyl-substituted Schiff-bases) afforded the corresponding Ru(II) carbonyl complexes [ L 2 Ru(CO) 2 ] 1a-1g in good yields. All the Ru complexes were well characterized by elemental analysis, FT-IR, NMR and HR-MS. The molecular structures of 1c, 1e and 1g were reconfirmed by X-ray crystallography. These complexes showed high activity in the selective oxidation of benzylic C-H bonds with tert -butylhydroperoxide (TBHP) under mild conditions to give aryl ketones in 60 %–98 % yields. This catalytic protocol proceeds at room temperature with low catalyst loading (1.0 mol%), displays broad functional-group compatibility and has potential application for industry-scale reactions. [Display omitted] [ABSTRACT FROM AUTHOR]

• Easily synthesized ligands and air- and moisture-stable Ni complexes. • Both aldehydes and ketones were efficiently hydrosilylated to the corresponding alcohols. • The present catalytic reaction carried out in room temperature and displayed excellent functional group tolerance. Treatment of Ni(OAc) 2 ⋅4H 2 O with 8-hydroxylquinoline-imine ligands [2-(ArN=HC)-8-OH]C 9 H 5 N (Ar = 2,6- i Pr 2 C 6 H 3 , L1H ; Ar = 2,4,6-(Me) 3 C 6 H 2 , L2H ; Ar = 4-MeC 6 H 4 , L3H and Ar = 4-ClC 6 H 4 , L4H) in refluxing EtOH afforded the dual-ligand coordinated nickel complexes [L 2 Ni] 1 - 4 , respectively. All the four nickel complexes were characterized by IR, elemental analysis and high-resolution mass spectrometry. Furthermore, the molecular structures of complexes 3 and 4 were confirmed by X-ray diffraction analysis. Complexes 1 - 4 were found to be efficient catalysts for hydrosilylation of aldehydes and ketones with PhSiH 3 as the hydrogen source. Various aromatic and aliphatic ketones and aldehydes were proven to be suitable substrates for such catalytic property, affording the corresponding alcohols in good to excellent yields. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] Four nickel complexes incorporating N,N,N -quinolinyl anilido-imine ligands based on ortho -C 6 H 4 F(CH = NAr) and 8-aminoquinoline, Ni[{2-[ArN = C(H)]C 6 H 4 }N(8-C 9 H 6 N)]Br (Ar = 2,6- i Pr 2 C 6 H 3 (1a), 2,4,6-(CH 3) 3 C 6 H 2 (1b), 4-BrC 6 H 4 (1c)) and Ni[{2-[ArN = C(H)]C 6 H 4 }N(8-C 9 H 6 N)] 2 (Ar = 4-ClC 6 H 4 (1d)) were synthesized and structurally characterized by HR-MS, IR, NMR spectroscopy and X-ray crystallography. These nickel(II) complexes were used in Suzuki-Miyaura coupling and exhibited moderate to excellent catalytic activity with a low catalyst loading of 2.0 mol%. [ABSTRACT FROM AUTHOR]

Five novel trinuclear ruthenium complexes [[PyCH＝C(RC6H4)O]2Ru3(CO)8] [R = 4-OMe (6), 4-Br (7), 4-CF3 (8)] and [[PyCH2CH(RC6H4)O]2Ru3(CO)8] [R = 2-Br (9), 2-CF3 (10)], were synthesized by treating Ru3(CO)12 with two equivalents of the corresponding pyridine-alcohols PyCH2CH(RC6H4)OH [1–5, R = 4-OMe, 4-Br, 4-CF3, 2-Br and 2-CF3] in refluxing toluene. The structures of 6–10 were fully characterized by IR and NMR spectroscopy, elemental analysis and single-crystal X-ray diffraction. They were found to be efficient catalysts for the oxidation of secondary alcohols by NMO, giving the corresponding ketones in good to excellent yields within 15 min, of which [PyCH＝C(4-OCH3C6H4)O]2Ru3(CO)8 (6) is the best. [ABSTRACT FROM AUTHOR]

Treatment of Cu(OAc) 2 ·H 2 O with salicylaldimine Schiff-base (C 9 H 6 N)N=CH(3,5- t Bu 2 C 6 H 2 OH) (L1H) , (Et 2 N)(CH 2) 2 N=CH(3,5- t Bu 2 C 6 H 2 OH) (L2H) , (2-C 5 H 4 N)CH 2 N=CH(3,5- t Bu 2 C 6 H 2 OH) (L3H) in refluxing ethanol afforded three mononuclear copper complexes [(L1)Cu(OAc)] (1), (L2)Cu(OAc) (2) and (L3)Cu(OAc) (3), respectively. The three new complexes were fully characterized using elemental analysis, IR and HR-MS, and X-ray diffraction analysis. They all exhibited efficient catalytic activity in the oxidation of primary and secondary alcohols into the corresponding carbonyl derivatives with hydrogen peroxide (H 2 O 2) as the oxidation agent. The catalytic system is operationally simple, clean and generates water as the only by-product.Three new mononuclear copper complexes supported by tridentate salicylaldimine Schiff-base ligands were successfully synthesized and their catalytic activity for the oxidation reaction of primary and secondary alcohols in the presence of H 2 O 2 as an oxidant reagent was researched. [Display omitted] Treatment of Cu(OAc) 2 ·H 2 O with salicylaldimine Schiff-base (C 9 H 6 N)N = CH(3,5- t Bu 2 C 6 H 2 OH) (L1H) , (Et 2 N)(CH 2) 2 N = CH(3,5- t Bu 2 C 6 H 2 OH) (L2H) , (2-C 5 H 4 N)CH 2 N = CH(3,5- t Bu 2 C 6 H 2 OH) (L3H) in refluxing ethanol afforded three mononuclear copper complexes [(L1)Cu(OAc)] (1), (L2)Cu(OAc) (2) and (L3)Cu(OAc) (3), respectively. The three new complexes were fully characterized using elemental analysis, IR and HR-MS, and X-ray diffraction analysis. They all exhibited efficient catalytic activity in the oxidation of primary and secondary alcohols into the corresponding carbonyl derivatives with hydrogen peroxide (H 2 O 2) as the oxidation agent. The catalytic system is operationally simple, clean and generates water as the only by-product. [ABSTRACT FROM AUTHOR]

Abstract: A synthetic route to a new polymeric platinum(II)-containing germylacetylene has been developed. Soluble and thermally stable platinum(II) polyyne polymer trans-[–Pt(PBu3)2C CGePh2C C–] n (P1) was prepared in good yield by CuI-catalyzed polymerization of trans-[Pt(PBu3)2Cl2] and Ph2Ge(C CH)2. We report the optical absorption and photoluminescence spectra of P1 and the results are compared with platinum(II) polyynes with purely acetylenic and other (hetero)aromatic conjugated units. Harvesting of organic triplet emission harnessed through the strong heavy-atom effect of Pt and Ge was examined. Polymer P1 was found to have a high optical bandgap (ca. 3.84 eV). The influence of metal and sp3-hybridized germyl-based conjugation interrupter on the intersystem crossing rate and the spatial extent of the lowest singlet and triplet excitons were fully elucidated. Our investigations indicate that a high-bandgap polymer P intrinsically gives rise to a very efficient phosphorescence with fast radiative decay. Remarkably, a simple single-step method was also established for the synthesis of platinum–germanium (PtGe) alloy nanoparticles using P1 as the polymer precursor and the resulting ceramic metal alloys have been characterized by powder X-ray diffraction, energy dispersive X-ray analysis and transmission electron microscopy. [Copyright &y& Elsevier]

Die Antwort liegt in der DNA: Es konnte nicht bestätigt werden, dass die Alkylierung eines bestimmten Proteins zur Cytotoxizität der Duocarmycine beiträgt, wie kürzlich berichtet wurde. Stattdessen weisen die Ergebnisse, wie z. B. ein von einem „klickbaren“ Analogon stammendes Fluoreszenzsignal, auf eine im Zellkern stattfindende Reaktion hin. [ABSTRACT FROM AUTHOR]

The answer lies in the DNA: Recent claims that the alkylation of a particular protein contributes to the cytotoxicity of the duocarmycins could not be substantiated. The evidence, like the fluorescent signal derived from a clickable analogue, points instead to a reaction occurring in the nucleus. [ABSTRACT FROM AUTHOR]

Abstract: Sixteen new thiazine–quinoline–quinones have been synthesised, plus one bicyclic analogue. These compounds inhibited neutrophil superoxide production in vitro with IC50s as low 60nM. Compounds with high in vitro anti-inflammatory activity were also tested in a mouse model of acute inflammation. The most active compounds inhibited both neutrophil infiltration and superoxide production at doses 2.5μmol/kg, highlighting their potential for development as novel NSAIDs. [Copyright &y& Elsevier]

Abstract: Several novel series of nitrile-containing fluoroquinolones with weakly basic amines are reported which have reduced potential for hERG (human ether-a-go-go gene) channel inhibition as measured by the dofetilide assay. The new fluoroquinolones are potent against both Gram-positive and fastidious Gram-negative strains, including Methicillin resistant Staphylococcus aureus and fluoroquinolone-resistant Streptococcus pneumoniae. Several analogs also showed low potential for human genotoxicity as measured by the clonogenicity test. Compounds 22 and 37 (designated PF-00951966 and PF-02298732, respectively), which had good in vitro activity and in vitro safety profiles, also showed good pharmacokinetic properties in rats. [Copyright &y& Elsevier]

The organocobalt complexes containing functionally substituted cyclopentadienyl ligands (η5-RC5H4)Co(PPh3)2 (1a, R=EtO2C; 1b, R=MeCO) were synthesized by reactions of the corresponding functionalized cyclopentadienides RC5H4Na with (PPh3)3CoCl in 65 and 85% yields, respectively. The ligand exchange reaction of 1a with PhC&z.tbnd6;CPh afforded (η5-EtO2CC5H4)Co(PPh3)( η2-PhC&z.tbnd6;CPh) (2a) in 72% yield, whereas (η5-RC5H4)Co(PPh3)2 (1a, R=EtO2C; 1b, R=MeCO; 1c, R=H) reacted with C60 through ligand exchange to give (η5-RC5H4)Co(PPh3)(η2-C60) (3a, R=EtO2C; 3b, R=MeCO; 3c, R=H) in 34–68% yields. 3a could be also obtained similarly by ligand exchange reaction of 2a with C60 in 83% yield. In addition, reaction of 2a or 3a with excess iodine I2 produced (η5-EtO2CC5H4)Co(PPh3)(I)2 (4a) in 90–91% yields. The new compounds 1a, 1b, 2a, 3a–3c and 4a were characterized by 1H-NMR, 31P-NMR, IR, UV–Vis spectra and elemental analysis, whereas the reverse saturable absorption properties of the organocobalt fullerene complexes 3a and 3c along with C60 were studied by Z-scan method. [Copyright &y& Elsevier]

The [MgBr]+ salts of the μ4-S-containing double-butterfly anions {(μ-RS)(μ-CO)[Fe2(CO)6]2(μ4-S)}− (1, R=Ph, p-MeC6H4) react in situ with CS2 followed by treatment of the corresponding intermediate [MgBr]+ salts of anions {(μ-RS)(μ-S&z.dbnd6;CS)[Fe2(CO)6]2(μ4-S)}− (m1) with ClCH2CO2Et to give μ4-S-containing double-butterfly iron carbonyl complexes (μ-RS)(μ-EtO2CCH2SC&z.dbnd6;S)[Fe2(CO)6]2(μ4-S) (2a, R=Ph; 2b, R=p-MeC6H4), whereas the in situ reaction of the [MgX]+ (X=I, Br) salts of anions 1 (R=Me, Et) with μ-S2Fe2(CO)6 followed by treatment of the corresponding intermediate salts of anions {(μ-RS)(μ-S)[Fe2(CO)6]3(μ4-S)2}− (m2) with PhC(O)Cl produces μ4-S-containing unsymmetrical triple-butterfly iron carbonyl complexes (μ-RS)[μ-PhC(O)S][Fe2(CO)6]3(μ4-S)2 (3a, R=Me; 3b, R=Et). More interestingly, the symmetrical μ4-S-containing triple-butterfly complexes (μ-RE)2[Fe2(CO)6]3(μ4-S)2 (5a, RE=EtS; 5b, RE=t-BuS; 5c, RE=PhSe; 5d, RE=p-MeC6H4Se) can be synthesized by reaction of an excess of the [Et3NH]+ salts of the μ-CO-containing single-butterfly anions [(μ-RE)(μ-CO)Fe2(CO)6]− (4) with μ-S2Fe2(CO)6 and subsequent treatment of the resulting mixture with SO2Cl2. While the function of an excessive 4 for production of 5a–d is proposed, products 2a,b, 3a,b and 5a–d have been characterized by elemental analysis, and IR and 1H NMR spectroscopy, as well as for 3b and 5b by X-ray diffraction techniques. [Copyright &y& Elsevier]

• Phosphine-free ligands, air- and moisture-stable catalysts. • Mild condition, broad substrate scope, environmentally benign methodology. • Highly efficient access to two kinds of aromatic N-heterocyclic compounds. Treatment of N,N,O-tridentate pyrazolyl-pyridinyl-alcohol ligands, 2-(CR1R2OH)-6-[3,5-(R3) 2 C 3 HN 2 ]C 5 H 3 N (R1 = R2 = Me, R3 = H (L1H); R1 = Me, R2 = Ph, R3 = H (L2H); R1 = R2 = Ph, R3 = H (L3H); R1 = R2 = R3 = Me (L4H)) with RuCl 3 •xH 2 O in refluxing EtOH afforded the corresponding Ru(III) complexes L 2 RuCl (1a - 1d), which were well characterized by IR, HR-MS and X-ray single crystal structural determination. These Ru complexes showed similarly high catalytic performance for both dehydrogenative couplings of 2-aminoarylmethanols with ketones and nitriles, giving the quinolines and quinazolines in good to excellent yields. This protocol provides an atom-economical and sustainable route to access various structurally important quinoline and quinazoline derivatives by using phosphine-free ligand based Ru catalysts. [Display omitted] [ABSTRACT FROM AUTHOR]

• A series of novel trinuclear ruthenium complexes were synthesized and well characterized. • All the Ru complexes are easily to prepared and stable to air and moisture. • The present catalytic system showed high efficiency for oxidation of secondary alcohols to give the ketones in good to excellent yields. A series of novel trinuclear ruthenium carbonyl complexes [ µ - ƞ 2-2-OC 6 H 4 -CH=N-Ar)] 2 Ru 3 (CO) 8 [Ar = Ph (8), C 6 H 4 -4-Me (9), C 6 H 4 -4-CF 3 (10), C 6 H 4 -4-Cl (11), C 6 H 3 -2,6-Me 2 (12), C 6 H 3 -2,6-Et 2 (13)] and [ µ - ƞ 2-2-OC 6 H 4 -CH=N-C 6 H 3 -2,6- i Pr 2 ]Ru 3 (CO) 9 (14) were designed and synthesized. All the seven novel complexes were fully characterized by elemental analysis, IR and NMR spectroscopy. Molecular structures of 8, 11, 13 and 14 were further confirmed by single-crystal X-ray diffraction. The catalytic performance of these complexes in the oxidation of secondary alcohols was explored and it was found the combination of such complexes and N -methylmorpholine-N-oxide (NMO) exhibits high catalytic activities for the oxidation of secondary alcohols, giving the corresponding carbonyl compounds in excellent yields. A series of novel trinuclear ruthenium carbonyl complexes supported by salicylaldimine ligands were successfully synthesized and their catalytic activity for oxidation of secondary alcohols was studied. Image, graphical abstract [ABSTRACT FROM AUTHOR]

Reaction of Ru 3 (CO) 12 with 2.0 equiv of RN = CH(3,5- t Bu 2 C 6 H 2 OH) (R = C 6 H 5 , L1 ; R = 4-MeC 6 H 4 , L2 ; R = 4-OMeC 6 H 4 , L3 ; R = 4-ClC 6 H 4 , L4 ; R = 4-BrC 6 H 4 , L5 ; R = 4-CF 3 C 6 H 4 , L6) in refluxing xylene afforded the corresponding bis-chelate Ru(II) complexes 1a–1f [RN = CH(3,5- t Bu 2 C 6 H 2 O)] 2 Ru(CO) 2 and one of the imine bonds reduced complexes {[RN = CH(3,5- t Bu 2 C 6 H 2 O)]-[RNH-CH 2 (3,5- t Bu 2 C 6 H 2 O)]}Ru(CO) 2 2a–2f. All the ruthenium complexes were fully characterized by NMR, IR and elemental analysis. In addition, the structures of complexes 1a–1f , 2b , 2d and 2f were further confirmed by single-crystal X-ray diffraction. When activated with N -methylmorpholine- N -oxide (NMO), these Ru complexes displayed high catalytic activities toward oxidation of both 1° and 2° alcohols. For most cases, the reaction can complete within 1 h in refluxing CH 3 CN. [ABSTRACT FROM AUTHOR]