Reactivity of Diruthenium Bisborylene Complexes: Formation of B-C and B-H Bonds via Borylene Ligand Coupling.

Thermal or photoinduced isomerization of diruthenium bridging bisborylene complexes [{Cp*(H)Ru}(μ-BAr)] (, Ar = Ph; , Ar = 3,4,5-FCH) led to -ruthenacarboranes and with newly formed B-C and B-H bonds. The reaction mechanism was analyzed by deuterium-labeling experiments and density functional theory calculations. Additionally, 2-fold B-H coupling between borylene and two hydrido ligands of can be achieved, assisted by Lewis base IPrMe to generate a dinuclear bridging borylene complex [(Cp*Ru)(μ-H)(μ-BPh)] ().

Hetero Diels-Alder reactions of isolable -borylenamines.

A new strategy for -borylenamines by reaction of 2-alkynyl benzyl azides with B(CF) was developed. This novel 1,3-carboboration reaction proceeded a 5- cyclization/formal 1,1-carboboration/B(CF) shift reaction sequence. Additionally, -borylenamines can undergo hetero Diels-Alder (HDA) reactions with a variety of dienophiles.

Bifunctional Ligand Enables Gold-Catalyzed Propargyl C-H Functionalization via Reactive Gold Allenylidene Intermediate.

Gold allenylidene species have been seldom exploited as reactive intermediates in synthetically versatile catalytic reactions. By employing alkynylbenziodoxoles as the substrates and bifunctional WangPhos as the metal ligand, this work demonstrated ready catalytic access to these intermediates of general substitution patterns and their electrophilic reactivities at the γ-carbon center with a diverse range of nucleophiles. The reaction is driven by the reductive decomposition of the benziodoxole moiety and achieves the replacement of a propargylic proton with an N/O/C-based nucleophile, hence realizing reactivity umpolung.

Directed S2 Glycosylation Employing an Amide-Functionalized 1-Naphthoate Platform Featuring a Selectivity-Safeguarding Mechanism.

This work implements a catalytic S2 glycosylation by employing an amide-functionalized 1-naphthoate platform as a latent glycosyl leaving group. Upon gold-catalyzed activation, the amide group enables the S2 process by directing the attack of the glycosyl acceptor via H-bonding interaction, which results in stereoinversion at the anomeric center. Unique in this approach is that the amide group also enables a novel safeguarding mechanism by trapping oxocarbenium intermediates and, hence, minimizing stereorandom S1 processes.

Reactivities of α-Oxo BMIDA Gold Carbenes Generated by Gold-Catalyzed Oxidation of BMIDA-Terminated Alkynes.

An oxidative strategy is reported to access α-oxo BMIDA gold carbenes directly from BMIDA-terminated alkynes. Besides offering expedient access to seldom studied boryl metal carbenes, these BMIDA gold carbene species undergo facile insertions into methyl, methylene, methine, and benzylic C-H bonds in the absence of the Thorpe-Ingold effect. They also undergo efficient OH insertion, cyclopropanation, and F-C alkylations.

Ruthenium tris(σ-B-H) borate complexes: synthesis, structure, and reactivity.

The coordination of the B-H bond to a transition metal is fundamentally intriguing due to its connection with the transition metal-mediated B-H bond activation mechanism and catalysis. Most of the reported examples are σ-borane/borate complexes containing one or two σ-B-H bonds. However, examples of compounds containing three σ-B-H bonds are still much rarer.

From trihydroborates to bisborylenes: a route to dinuclear bisborylene complexes.

A new route for the synthesis of dinuclear bisborylene complexes was described. A series of novel diruthenium bisborylenes were prepared through unprecedented triple B-H oxidative addition of trihydroborates with concomitant hydrogen liberation. Conversion of trihydroborates to bisborylenes involved the formation of tris(σ-B-H) borate as the crucial intermediate stage.

Synthesis of -acyl furanosides the cross-coupling of glycosyl esters with carboxylic acids.

-Acyl furanosides are versatile synthetic precursors to a variety of natural products, nucleoside analogues, and pharmaceutical molecules. This report addresses the unmet challenge in preparing -acyl furanosides by developing a cross-coupling reaction between glycosyl esters and carboxylic acids. A key step is the photoredox activation of the glycosyl ester, which promotes the homolysis of the strong anomeric C-O bond through CO evolution to afford glycosyl radicals.

Facile synthesis of air-stable heterobimetallic osmium-silver hydride complexes.

The synthesis and characterization of air-stable heterobimetallic Os-Ag hydrides are described. All of the new heterobimetallic Os-Ag hydrides are neutral, and the generated and presynthesized -[Os](H)-CC-R units in these frameworks act as organometallic bidentate chelating ligands coordinating with the AgPPh cation, which makes these complexes more stable. Our results provide a new synthetic route for the construction of stable heterobimetallic complexes.

B-H and O-H bonds activation a single electron transfer of frustrated radical pairs.

The rare examples of B-H bond activation in a frustrated radical pair regime have been observed by treatment of TEMPO radicals with Piers' borane HB(C6F5)2 or bis-borane, respectively. The resulting concomitant formation of zwitterionic products and geminal N/B frustrated Lewis pairs implied a one electron process. In addition, the reaction of a TEMPO/B(C6F5)3 pair with H2O·B(C6F5)3 was assumed to involve one-electron reduction of water.

Rivastigmine Transdermal Patch Treatment for Moderate to Severe Cognitive Impairment in Veterans with Traumatic Brain Injury (RiVET Study): A Randomized Clinical Trial.

Cognitive impairment is common in veterans with histories of traumatic brain injury (TBI). Cholinergic deficits have been hypothesized as contributors to this impairment. We report the effects of cholinesterase inhibitor rivastigmine transdermal patch treatment in veterans with TBI and post-traumatic memory impairment.

Diastereoselective Synthesis of Aryl C-Glycosides from Glycosyl Esters via C-O Bond Homolysis.

C-aryl glycosyl compounds offer better in vivo stability relative to O- and N-glycoside analogues. C-aryl glycosides are extensively investigated as drug candidates and applied to chemical biology studies. Previously, C-aryl glycosides were derived from lactones, glycals, glycosyl stannanes, and halides, via methods displaying various limitations with respect to the scope, functional-group compatibility, and practicality.

Plaque Regression and Endothelial Progenitor Cell Mobilization With Intensive Lipid Elimination Regimen (PREMIER).

Background: Low-density lipoproteins (LDLs) are removed by extracorporeal filtration during LDL apheresis. It is mainly used in familial hyperlipidemia. The PREMIER trial (Plaque Regression and Progenitor Cell Mobilization With Intensive Lipid Elimination Regimen) evaluated LDL apheresis in nonfamilial hyperlipidemia acute coronary syndrome patients treated with percutaneous coronary intervention.

Veterans Affairs Low-vision Intervention Trial II: One-year Follow-up.

Significance: One-year follow-up is recommended for patients with macular diseases to assess functional changes associated with disease progression and to modify low-vision (LV) treatment plans, if indicated.

Purpose: The purpose of this study was to observe 255 patients with macular diseases who received LV rehabilitation (rehabilitation with a therapist) or basic LV services (LV devices dispensed without therapy) during Veterans Affairs Low-vision Intervention Trial II after the trial ended at 4 months until 1-year follow-up.

Methods: The primary outcome measure was visual ability measured with the 48-item Veterans Affairs Low-vision Visual Functioning Questionnaire.

Cobalt-Catalyzed Trifluoromethoxylation of Epoxides.

A catalytic ring-opening reaction of epoxides by nucleophilic trifluoromethoxylation of trifluoromethyl arylsulfonate has been developed based on the use of a cobalt catalyst. This reaction provides an efficient, simple route for directly construction of a wide range of vicinal trifluoromethoxyhydrins under mild conditions. In addition, this method can convert terminal epoxides into target products with good chemo- and regioselectivity.

Economic Evaluation of Low-Vision Rehabilitation for Veterans With Macular Diseases in the US Department of Veterans Affairs.

Importance: Examining costs and consequences of different low-vision (LV) programs provides important information about resources needed to expand treatment options efficiently.

Objective: To examine the costs and consequences of LV rehabilitation or basic LV services.

Design, Setting, And Participants: The US Department of Veterans Affairs (VA) Low Vision Intervention Trial (LOVIT) II was conducted from September 27, 2010, to July 31, 2014, at 9 VA facilities and included 323 veterans with macular diseases and a best-corrected distance visual acuity of 20/50 to 20/200.

Combining photoredox and silver catalysis for azidotrifluoromethoxylation of styrenes.

The first example of an azidotrifluoromethoxylation of styrenes has been achieved by synergistic visible-light-mediated photoredox and silver catalysis. Trifluoromethyl arylsulfonate (TFMS) and the Zhdankin reagent were used as the trifluoromethoxylation reagent and the azide source, respectively. A good functional group tolerance and mild reaction conditions of this method are applicable to late-stage azidotrifluoromethoxylation of complex small molecules.

Pd(II)-NHDC-Functionalized UiO-67 Type MOF for Catalyzing Heck Cross-Coupling and Intermolecular Benzyne-Benzyne-Alkene Insertion Reactions.

A novel palladium N-heterocyclic bis-carbene dicarboxylate ligand (Pd-NHDC-HL) was successfully synthesized. In addition, an Pd-NHDC-containing UiO-67 type MOF (UiO-67-Pd-NHDC) was prepared on the basis of a size-matched ligand mixture of biphenyl-4,4'-dicarboxylic acid/Pd-NHDC-HL (9/1) and ZrCl under solvothermal conditions. The obtained UiO-67-Pd-NHC MOF can be a highly heterogeneous catalyst to promote Heck cross-coupling and intermolecular benzyne-benzyne-alkene insertion reactions.

Outcomes of the Veterans Affairs Low Vision Intervention Trial II (LOVIT II): A Randomized Clinical Trial.

Importance: Randomized clinical trials are needed to compare effectiveness and cost-effectiveness of different low-vision (LV) programs.

Objective: To determine the value of adding LV rehabilitation with a therapist compared with LV services without intervention.

Design, Setting, And Participants: A randomized clinical trial was conducted from September 27, 2010, to July 31, 2014, of 323 veterans with macular diseases and best-corrected distance visual acuity (BCDVAbetter-eye) of 20/50 to 20/200.

A N-heterocyclic tetracarbene Pd(ii) moiety containing a Pd(ii)-Pb(ii) bimetallic MOF for three-component cyclotrimerization via benzyne.

A novel Pd(ii)-Pb(ii) bimetallic metal-organic framework Pd(ii)-Pb(ii)-MOF (B) which contains an N-heterocyclic tetracarbene Pd(ii) moiety was synthesized based on a chelating N-heterocyclic dicarbene Pd(ii)-NHDC ligand (A) under solvothermal conditions. It can be a highly active heterogeneous catalyst for three-component cyclotrimerization via benzyne species.

Satellite observations and modeling of oil spill trajectories in the Bohai Sea.

On June 4 and 17, 2011, separate oil spill accidents occurred at two oil platforms in the Bohai Sea, China. The oil spills were subsequently observed on different types of satellite images including SAR (Synthetic Aperture Radar), Chinese HJ-1-B CCD and NASA MODIS. To illustrate the fate of the oil spills, we performed two numerical simulations to simulate the trajectories of the oil spills with the GNOME (General NOAA Operational Modeling Environment) model.

The effectiveness of low-vision rehabilitation in 2 cohorts derived from the veterans affairs Low-Vision Intervention Trial.

Objective: To evaluate the effectiveness of low-vision rehabilitation in 2 cohorts derived from the Veterans Affairs Low-Vision Intervention Trial.

Methods: In a prospective study, we observed 44 participants randomly assigned to outpatient low-vision rehabilitation who did not receive additional treatment after the trial ended at 4-month follow-up and 56 participants randomly assigned to the waiting-list control group and thereafter to standard therapy. The outcome measures included visual ability domains (reading, mobility, visual information processing, and visual motor skills) and overall visual ability estimated from difficulty ratings using the 48-item Veterans Affairs Low-Vision Visual Functioning Questionnaire.

A clinician's guide to patient selection for watchful waiting management of inguinal hernia.

Objective: The goal of this study was to assist surgeons in managing patients with minimally symptomatic inguinal hernia by identifying characteristics that predict crossover to surgery or worsening of hernia symptoms.

Background: Randomized trials have suggested that watchful waiting management of minimally symptomatic inguinal hernia is an acceptable alternative to surgical repair. However, these trials found that roughly a quarter of patients would elect for repair in the first 2 years, suggesting that not all patients are good candidates for watchful waiting.

Predictive value of the Disorders of Consciousness Scale (DOCS).

Objective: To examine the predictive validity of measures of neurobehavioral change derived from the Disorders of Consciousness Scale (DOCS) for predicting return to consciousness 4, 8, and 12 months after severe brain injury (BI).

Design: Prospective observational predictive validity study

Setting: Inpatient rehabilitation hospitals and postrehabilitation residence

Participants: A total of 113 persons with a mean age of 38 +/- 17.8 years who were unconscious for >28 days consecutively after severe BI; 73% (83/113) with traumatic BI and 27% (30/113) with other BI.