Ru–Ag and Ru–Au dicarbene complexes from an abnormal carbene ruthenium system

The first complexes containing an anionic dicarbene connected to two different d-block elements are reported. The synthetic pathway entails metalation and transmetalation reactions, starting from a cationic abnormal Ru-NHC complex

Effects of Anacetrapib in Patients with Atherosclerotic Vascular Disease

BACKGROUND: Patients with atherosclerotic vascular disease remain at high risk for cardiovascular events despite effective statin-based treatment of low-density lipoprotein (LDL) cholesterol levels. The inhibition of cholesteryl ester transfer protein (CETP) by anacetrapib reduces LDL cholesterol levels and increases high-density lipoprotein (HDL) cholesterol levels. However, trials of other CETP inhibitors have shown neutral or adverse effects on cardiovascular outcomes. METHODS: We conducted a randomized, double-blind, placebo-controlled trial involving 30,449 adults with atherosclerotic vascular disease who were receiving intensive atorvastatin therapy and who had a mean LDL cholesterol level of 61 mg per deciliter (1.58 mmol per liter), a mean non-HDL cholesterol level of 92 mg per deciliter (2.38 mmol per liter), and a mean HDL cholesterol level of 40 mg per deciliter (1.03 mmol per liter). The patients were assigned to receive either 100 mg of anacetrapib once daily (15,225 patients) or matching placebo (15,224 patients). The primary outcome was the first major coronary event, a composite of coronary death, myocardial infarction, or coronary revascularization. RESULTS: During the median follow-up period of 4.1 years, the primary outcome occurred in significantly fewer patients in the anacetrapib group than in the placebo group (1640 of 15,225 patients [10.8%] vs. 1803 of 15,224 patients [11.8%]; rate ratio, 0.91; 95% confidence interval, 0.85 to 0.97; P=0.004). The relative difference in risk was similar across multiple prespecified subgroups. At the trial midpoint, the mean level of HDL cholesterol was higher by 43 mg per deciliter (1.12 mmol per liter) in the anacetrapib group than in the placebo group (a relative difference of 104%), and the mean level of non-HDL cholesterol was lower by 17 mg per deciliter (0.44 mmol per liter), a relative difference of -18%. There were no significant between-group differences in the risk of death, cancer, or other serious adverse events. CONCLUSIONS: Among patients with atherosclerotic vascular disease who were receiving intensive statin therapy, the use of anacetrapib resulted in a lower incidence of major coronary events than the use of placebo. (Funded by Merck and others; Current Controlled Trials number, ISRCTN48678192 ; ClinicalTrials.gov number, NCT01252953 ; and EudraCT number, 2010-023467-18 .)

Tandem Suzuki-Miyaura/transfer hydrogenation reaction catalyzed by a Pd-Ru complex bearing an anionic dicarbene

A hetero-bimetallic Pd-Ru N-Heterocyclic Dicarbene (NHDC) complex was synthesized from a Ag-Ru complex by transmetalation. The Pd-Ru system displays high catalytic activity in tandem Suzuki-Miyaura cross-coupling/transfer hydrogenation reaction of bromoaryl ketones with boronic acids in toluene and 2-propanol in the presence of KOH

Controlling Coordination Geometries: Ru–Carbene Complexes with Tetra-NHC Ligands

The synthesis of the first ruthenium­(II) complexes bearing open-chain tetra-<i>N</i>-heterocyclic carbene (tetra-NHC) ligands via in situ transmetalation is described. The ruthenium complexes show differing coordination geometries depending on the length of the alkyl linker. Replacement of the two <i>cis</i> acetonitrile ligands in the methylene bridged ruthenium complex by nucleophiles also influences the coordination geometry. Both structural motifs were evaluated in transfer hydrogenation (TH) of acetophenone, and in particular the sawhorse-type coordinated system exhibits remarkable activity with turnover frequencies of more than 100 000 h^–1

On the Concept of Hemilability: Insights into a Donor-Functionalized Iridium(I) NHC Motif and Its Impact on Reactivity

Novel iridium­(I) complexes bearing N-donor-functionalized N-heterocyclic carbene ligands were synthesized. Although hemilabile coordination of the attached donor is considered beneficial in catalysis, no detailed study of this phenomenon in these systems is available to date. The present report provides insight into the hemilabile bonding properties of a <i>N</i>,<i>N</i>′-bis­(pyridin-2-yl)-imidazolylidene (NCN) ligand motif on iridium­(I). In most cases, the presented compounds exhibit rare fluxional hemilabile coordination of the N donor, and remarkable performance in catalytic transfer hydrogenation is observed. Further, extensive reactivity studies often led to unexpected products

Age-related changes in general and sexual health in middle-aged and older men: results from the European Male Ageing Study (EMAS)

ABSTRACT Introduction.  Limited information is available concerning the general and sexual health status of European men. Aim.  To investigate the age-related changes in general and sexual health in middle-aged and older men from different countries of the European Union. Methods.  This is a cross-sectional multicenter survey performed on a sample of 3,369 community-dwelling men aged 40–79 years old (mean 60 ± 11 years). Subjects were randomly selected from eight European centers including centers from nontransitional (Florence [Italy], Leuven [Belgium], Malmö[Sweden], Manchester [United Kingdom], Santiago de Compostela [Spain]) and transitional countries (Lodz [Poland], Szeged [Hungary], Tartu [Estonia]). Main Outcome Measures.  Different parameters were evaluated including the Beck's Depression Inventory for the quantification of depressive symptoms, the Short Form-36 Health Survey for the assessment of the quality of life (QoL), the International Prostate Symptom Score for the evaluation of lower urinary tract symptoms, and the European Male Ageing Study sexual function questionnaire for the study of sexual function. Results.  More than 50% of subjects reported the presence of one or more common morbidities. Overall, hypertension (29%), obesity (24%), and heart diseases (16%) were the most prevalent conditions. Around 30% of men reported erectile dysfunction (ED) and 6% reported severe orgasmic impairment, both of which were closely associated with age and concomitant morbidities. Only 38% of men reporting ED were concerned about it. Furthermore, concern about ED increased with age, peaking in the 50–59 years age band, but decreased thereafter. Men in transitional countries reported a higher prevalence of morbidities and impairment of sexual function as well as a lower QoL. Conclusion.  Sexual health declined while concomitant morbidities increased in European men as a function of age. The burden of general and sexual health is higher in transitional countries, emphasizing the need to develop more effective strategies to promote healthy aging for men in these countries