Tuning the Selectivity of Catalytic Nitrile Hydrogenation with Phase-Controlled Co Nanoparticles Prepared by Hydrosilane-Assisted Method.

Cobalt (Co) is a promising candidate to replace noble metals in the hydrogenation process, which is widely employed in the chemical industry. Although the catalytic performance for this reaction has been considered to be significantly dependent on the Co crystal phase, no satisfactory systematic studies have been conducted, because it is difficult to synthesize metal nanoparticles that have different crystalline structures with similar sizes. Here we report a new method for the synthesis of cobalt nanoparticles using hydrosilane as a reducing agent (hydrosilane-assisted method). This new method uses 1,3-butanediol and propylene glycol to successfully prepare fcc and hcp cobalt nanoparticles, respectively. These two types of Co nanoparticles have similar sizes and surface areas. The hcp Co nanoparticles exhibit higher catalytic performance than fcc nanoparticles for the hydrogenation of benzonitrile under mild conditions. The present hcp Co catalyst is also effective for highly selective benzyl amine production from benzonitrile without ammonia addition, whereas many catalytic systems require ammonia addition for selective benzyl amine production. Mechanistic studies revealed that the fast formation of the primary amine and the prevention of condensation and secondary amine hydrogenation promote selective benzonitrile hydrogenation for benzylamine over hcp Co nanoparticles.

Successful coil embolisation of tortuous portosystemic venous shunts using a steerable microcatheter in a patient with polysplenia after a Fontan-type operation.

Portosystemic venous shunts occur in patients with polysplenia after the Fontan operation. In the long term, these shunts are associated with hyperammonaemia and portal-systemic encephalopathy. Since some shunts are long and tortuous, catheter interventions to close them could be challenging. Instead, a steerable microcatheter could be used for coil embolisation of tortuous portosystemic venous shunts.

[Effective Treatment for Empyema with Fistula by Negative Pressure Wound Therapy:Report of a Case].

A 54-year-old male with alcoholic cirrhosis and diabetes mellitus was referred to our hospital for the treatment of right pleural empyema with fistula. Despite performing a simple suture closure of the pulmonary fistula, air leakage occurred one week after surgery. Hence, we covered the fistula with a pediculed muscle flap associated with an open window thoracostomy. After 32 days of gauze drainage, negative pressure wound therapy( NPWT) was introduced for reducing the residual pleural space. A chest computed tomography( CT) scan showed almost the full expansion of the lung after undergoing 98 days of NPWT. The patient was discharged from the hospital four months after thoracostomy.

Risk factors of mFOLFOX6-induced hyperammonemia in patients with colorectal cancer: an observational study.

BACKGROUND: FOLFOX therapy, a standard treatment for colorectal cancer (CRC), causes a rare, but serious adverse event, hyperammonemia. However, the risk factors of hyperammonemia remain unknown. METHODS: We examined 74 patients who received mFOLFOX6 therapy with or without biologics for CRC between April 2013 and March 2018 in Yaizu City Hospital. Clinicopathological factors were retrospectively reviewed in association with hyperammonemia, and risk factors of hyperammonemia during mFOLFOX6 therapy were analyzed in 32 patients with the available data. RESULTS: Seven patients developed hyperammonemia, with onset exclusively on day 2 or 3 in the first cycle of therapy. They were treated with branched chain amino acid administration and hydration; however, one patient with stage G4 chronic kidney disease (CKD) died. By multivariate analysis, estimated glomerular filtration rate (eGFR) < 60 mL/min/1.73 m2 was independently associated with hyperammonemia during FOLFOX therapy (odds ratio: 9.0, p = 0.040). CONCLUSIONS: Reduced eGFR is considered a risk factor of developing hyperammonemia during FOLFOX therapy. Serum ammonia levels should be monitored especially during the first cycle of FOLFOX therapy in patients with CKD stage G3 or higher.

[Experience with High-grade Fetal Lung Adenocarcinoma;Report of a Case].

A 61-year-old woman, who was revealed to have a 11 mm pulmonary nodule in the right middle lobe by computed tomography, was diagnosed with adenocarcinoma using bronchoscopy. Fluorodeoxyglucose-positron emission tomography (FDG-PET) showed FDG accumulation in the tumor, with a maximum standardized uptake value( SUVmax) of 2.47. Therefore, she underwent thoracoscopic right middle lobectomy. Histopathological examination revealed invasive growth of cylindrical tumor cells with clear glycogen-filled cytoplasm and a relatively high-grade nuclear atypia in tubulopapillary structures; no morula was observed. Immunohistochemically, the membranes of the tumor cells were positively stained for ß-catenin, indicating high-grade fetal adenocarcinoma (pT1bN0M0, pathologic stageⅠA2). The postoperative course was uneventful, without recurrence 6 months after surgery.

[Postoperative Chylothorax Likely to be Successfully Treated by Lymphangiography;Report of a Case].

A 74-year-old man underwent right upper lobectomy and systemic lymph node dissection with video-assisted thoracoscopic surgery. Chylothorax occurred on postoperative day (POD) 1st. Under fasting management, the patient underwent pleurodesis on POD 5th and 7th, subcutaneous octreotide acetate injection on POD 6th, and lymphangiography on POD 9th. The amount of drainage decreased on POD 10th, and the drainage tube was removed on POD 12nd. Lymphangiography has been reported as one of effective procedures to treat postoperative chylothorax. The present case is also considered to be successfully treated by lymphangiography.

Electronic Effect of Ruthenium Nanoparticles on Efficient Reductive Amination of Carbonyl Compounds.

Highly selective synthesis of primary amines over heterogeneous catalysts is still a challenge for the chemical industry. Ruthenium nanoparticles supported on Nb2O5 act as a highly selective and reusable heterogeneous catalyst for the low-temperature reductive amination of various carbonyl compounds that contain reduction-sensitive functional groups such as heterocycles and halogens with NH3 and H2 and prevent the formation of secondary amines and undesired hydrogenated byproducts. The selective catalysis of these materials is likely attributable to the weak electron-donating capability of Ru particles on the Nb2O5 surface. The combination of this catalyst and homogeneous Ru systems was used to synthesize 2,5-bis(aminomethyl)furan, a monomer for aramid production, from 5-(hydroxymethyl)furfural without a complex mixture of imine byproducts.

[Mediastinal Thyroid Carcinoma;Report of a Case].

71-year-old woman was pointed out to have an asymptomatic mediastinal tumor. Chest computed tomography(CT) showed a well-demarcated mass measuring 7 cm in diameter in the anterior mediastinum. We resected the mass through a median sternotomy. The tumor had a clear margin without invasion to the surrounding tissue and did not show continuity with the cervical thyroid gland. Histopathologically, the tumor was diagnosed as follicular thyroid carcinoma with capsular invasion. This is an exceptionally rare case.

Triply Halide-Bridged Dinuclear Iridium(III) Complexes with Chiral Diphosphine Ligands as New Easy-to-Handle Iridium Catalysts for Asymmetric Hydrogenation of Imines and N-Heteroaromatics.

Iridium(III) complexes bearing chiral ligands have proved to be active species in asymmetric hydrogenation of C=N bonds, though there are only a few iridium(III) precursors. We prepared triply halide-bridged dinuclear iridium complexes bearing chiral diphosphine ligands by simple treatment of the iridium(I) precursor, chiral diphosphine, and aqueous hydrogen halide. The strong advantage of these dinuclear iridium complexes is that they are air and moisture stable, leading to easy handling in asymmetric synthesis. The dinuclear iridium complexes exhibited high catalytic activity toward asymmetric hydrogenation of imines and N-heteroaromatics. Moreover, we demonstrated the application of triply halide-bridged dinuclear ruthenium(II) and rhodium(III) catalyst precursors for the asymmetric hydrogenation of ketonic substrates and simple olefins, respectively.

Asymmetric Allylic Alkylation of ß-Ketoesters with Allylic Alcohols by a Nickel/Diphosphine Catalyst.

Asymmetric allylic alkylation of ß-ketoesters with allylic alcohols catalyzed by [Ni(cod)2]/(S)-H8-BINAP was found to be a superior synthetic protocol for constructing quaternary chiral centers at the α-position of ß-ketoesters. The reaction proceeded in high yield and with high enantioselectivity using various ß-ketoesters and allylic alcohols, without any additional activators. The versatility of this methodology for accessing useful and enantioenriched products was demonstrated.

Chloride-Bridged Dinuclear Rhodium(III) Complexes Bearing Chiral Diphosphine Ligands: Catalyst Precursors for Asymmetric Hydrogenation of Simple Olefins.

Efficient rhodium(III) catalysts were developed for asymmetric hydrogenation of simple olefins. A new series of chloride-bridged dinuclear rhodium(III) complexes 1 were synthesized from the rhodium(I) precursor [RhCl(cod)]2 , chiral diphosphine ligands, and hydrochloric acid. Complexes from the series acted as efficient catalysts for asymmetric hydrogenation of (E)-prop-1-ene-1,2-diyldibenzene and its derivatives without any directing groups, in sharp contrast to widely used rhodium(I) catalytic systems that require a directing group for high enantioselectivity. The catalytic system was applied to asymmetric hydrogenation of allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones. Control experiments support the superiority of dinuclear rhodium(III) complexes 1 over typical rhodium(I) catalytic systems.

Enhancing effects of salt formation on catalytic activity and enantioselectivity for asymmetric hydrogenation of isoquinolinium salts by dinuclear halide-bridged iridium complexes bearing chiral diphosphine ligands.

Asymmetric hydrogenation of 1- and 3-substituted and 1,3-disubstituted isoquinolinium chlorides using triply halide-bridged dinuclear iridium complexes [{Ir(H)(diphosphine)}2 (µ-Cl)3 ]Cl has been achieved by the strategy of HCl salt formation of isoquinolines to afford the corresponding chiral 1,2,3,4-tetrahydroisoquinolines (THIQs) in high yields and with excellent enantioselectivities after simple basic work-up. The effects of salt formation have been investigated by time-course experiments, which revealed that the generation of isoquinolinium chlorides clearly prevented formation of the catalytically inactive dinuclear trihydride complex, which was readily generated in the catalytic reduction of salt-free isoquinoline substrates. Based on mechanistic investigations, including by (1) H and (31) P{(1) H} NMR studies and the isolation and characterization of several intermediates, the function of the chloride anion of the isoquinolinium chlorides has been elucidated, allowing us to propose a new outer-sphere mechanism involving coordination of the chloride anion of the substrates to an iridium dihydride species along with a hydrogen bond between the chloride ligand and the N-H proton of the substrate salt.

Pentacoordinated carboxylate π-allyl nickel complexes as key intermediates for the Ni-catalyzed direct amination of allylic alcohols.

Direct amination of allylic alcohols with primary and secondary amines catalyzed by a system made of [Ni(1,5-cyclooctadiene)2 ] and 1,1'-bis(diphenylphosphino)ferrocene was effectively enhanced by adding nBu4 NOAc and molecular sieves, affording the corresponding allyl amines in high yield with high monoallylation selectivity for primary amines and high regioselectivity for monosubstituted allylic alcohols. Such remarkable additive effects of nBu4 NOAc were elucidated by isolating and characterizing some nickel complexes, manifesting the key role of a charge neutral pentacoordinated η(3) -allyl acetate complex in the present system, in contrast to usual cationic tetracoordinated complexes earlier reported in allylic substitution reactions.

Construction of Tertiary Chiral Centers by Pd-catalyzed Asymmetric Allylic Alkylation of Prochiral Enolate Equivalents.

The palladium-catalyzed decarboxylative allylic alkylation of enol carbonates derived from lactams and ketones is described. Employing these substrates with an electronically tuned Pd catalyst system trisubstituted chiral centers are produced. These stereocenters have been previously challenging to achieve using Pd complex/chiral P-N ligand systems.

[Purtscher's retinopathy following blunt chest compression].

Following chest or abdominal injury, acute blurring of vision occurs without direct eye injury. This disease is known as Purtscher's retinopathy. A 74-year-old man suffered blunt chest injury by air bag inflation at traffic accident. Next morning, he suddenly complained of visual abnormality. An ophthalmoscopy revealed multiple cotton-wool exudation and retinal edema. He was diagnosed as Purtscher's retinopathy. The symptoms of soft exudation and retinal edema gradually resolved. The visual acuity gradually improved, but not reached to the previous level. We must be aware of this retinopathy, since this is rare but sometimes sight-threatening condition.

Air-Stable Ni Catalysts Prepared by Liquid-Phase Reduction Using Hydrosilanes for Reactions with Hydrogen.

The liquid-phase reduction method for the preparation of metal nanoparticles (NPs) by the reduction of metal salts or metal complexes in a solvent with a reducing agent is widely used to prepare Ni NPs that exhibit high catalytic activity in various organic transformations. Intensive research has been conducted on control of the morphology and size of Ni NPs by the addition of polymers and long-chain compounds as protective agents; however, these agents typically cause a decrease in catalytic activity. Here, we report on the preparation of Ni NPs using hydrosilane (Ni-Si) as a reducing agent and a size-controlling agent. The substituents on silicon can control not only the size but also the crystal phase of the Ni NPs. The prepared Ni NPs exhibited high catalytic performance for the hydrogenation of unsaturated compounds, aromatics, and heteroaromatics to give the corresponding hydrogenated products in high yields. The unique feature of Ni catalysts prepared by the hydrosilane-assisted method is that the catalysts can be handled under air as opposed to conventional Ni catalysts such as Raney Ni. Characterization studies indicated that the surface hydroxide was reduced under the catalytic reaction conditions with H2 at around 100 °C and with the assistance of organosilicon compounds deposited on the catalyst surface. The hydrosilane-assisted method presented here could be applied to the preparation of supported Ni catalysts (Ni-Si/support). The interaction between the Ni NPs and a metal oxide support enabled the direct amination of alcohols with ammonia to afford the primary amine selectively.

Laparoscopic repair for internal hernia associated with colostomy: a case report.

A 63-year-old woman was admitted with abdominal pain two months after laparoscopic abdominoperineal resection for rectal cancer. Computed tomography revealed dilated small intestine had passed through a defect between the lifted sigmoid colon and abdominal wall. She was diagnosed with small bowel obstruction without strangulation due to internal hernia and managed nonoperatively based on her wish. Recurrence of intestinal obstruction occurred for which curative surgery was performed laparoscopically. The herniated intestine was restored to the normal position, and the hernia orifice was closed using barbed suture, on laparoscopic management. Internal hernia is a rare complication after colostomy that requires surgical management. Although laparoscopic approach on re-operation is difficult, laparoscopic surgery may be suitable for patients with IHAC in terms of required less use of adhesiolysis.

Rhodium-catalyzed carbon-silicon bond activation for synthesis of benzosilole derivatives.

A rhodium-catalyzed coupling reaction of 2-trimethylsilylphenylboronic acid with internal alkynes is developed for the synthesis of 2,3-disubstituted benzosilole derivatives. A range of functional groups, encompassing ketones, esters, amines, aryl bromides, and heteroarenes, are compatible, which provides rapid access to diverse benzosiloles. Sequential 2-fold coupling enables modular synthesis of asymmetrically substituted 1,5-dihydro-1,5-disila-s-indacene, a π-extended molecule of interest in organic electronics. In terms of the mechanism, the reaction involves cleavage of a C(alkyl)-Si bond in a trialkylsilyl group, which normally requires extremely harsh conditions for activation. Mechanistic studies, including effects of substituents, reveal that C-Si bond cleavage does not proceed through a hypercoordinated silicon species, but rather through a rhodium-mediated activation process. The potential use of the reaction in catalytic asymmetric synthesis of Si-chiral benzosiloles is also demonstrated.

Rhodium(I)-catalyzed borylation of nitriles through the cleavage of carbon-cyano bonds.

The reaction of aryl cyanides with diboron in the presence of a rhodium/Xantphos catalyst and DABCO affords arylboronic esters via carbon-cyano bond cleavage. This unprecedented mode of reactivity for a borylrhodium species allows the regioselective introduction of a boryl group in a late stage of synthesis.