Electrooxidative 1,3-Oxo/Carboamination of Arylcyclopropanes.

Herein, the work demonstrates an electrochemically paired electrolysis approach facilitating the efficient achievement of the electrooxidative 1,3-oxo/carboamination of arylcyclopropanes under mild conditions. The formation of 1,3-arylamination of arylcyclopropanes involves commercially available amine redox mediators through a radical-radical process. In addition, the successful execution of β-amino ketones also occurs under atmospheric conditions.

Electrooxidative Fluorofunctionalization of Arylcyclopropanes.

The work herein demonstrates the viability of an electrochemical oxidative protocol for the expedient realization of 1,3-fluorofunctionalization of arylcyclopropanes under catalyst- and oxidant-free conditions. Given the relatively low nucleophilicity of fluoride ion, the counterintuitive outcome that the ring-opening is initiated by nucleophilic fluorination is rationalized by invoking tight ion pair between aryl radical cation and BF counterion. By integrating alcohols, acids, and N-heterocycles as the terminating nucleophiles, straightforward 1,3-fluorooxygenation and 1,3-fluoroamination are smoothly achieved.

Ni-Catalyzed Reductive Dibenzylation of Trifluoromethylalkenes for CF-Containing All-Carbon Quaternary Center Construction.

A Ni-catalyzed reductive dicarbofunctionalization of α-CF styrenes with benzyl bromides has been accomplished. This transformation obviates the commonly facile β-F elimination effectively and enables the creation of CF-substituted all-carbon quaternary centers of pharmaceutical interests. Preliminary mechanistic studies suggest a pathway consisting of benzyl radical addition and subsequent nickel-mediated benzylation of the resulting α-CF-embedded tertiary C radical.

Sugemalimab versus placebo after concurrent or sequential chemoradiotherapy in patients with locally advanced, unresectable, stage III non-small-cell lung cancer in China (GEMSTONE-301): interim results of a randomised, double-blind, multicentre, phase 3 trial.

Background: A substantial proportion of patients with unresectable stage III non-small-cell lung cancer (NSCLC) cannot either tolerate or access concurrent chemoradiotherapy, so sequential chemoradiotherapy is commonly used. We assessed the efficacy and safety of sugemalimab, an anti-PD-L1 antibody, in patients with stage III NSCLC whose disease had not progressed after concurrent or sequential chemoradiotherapy.

Methods: GEMSTONE-301 is a randomised, double-blind, placebo-controlled, phase 3 trial in patients with locally advanced, unresectable, stage III NSCLC, done at 50 hospitals or academic research centres in China.

Selective C-F Bond Allylation of Trifluoromethylalkenes.

Selective C-F bond functionalization of CF group represents an appealing strategy for the incorporation of pharmaceutically privileged difluoromethylene moiety. Despite the recent significant advancement attained in the functionalization of Ar-CF molecules, prescriptions amenable for alkenyl-CF congeners remain sufficiently inadequate. Herein, we report a strategically novel protocol for the C-F bond elaboration of trifluoromethylalkene derivatives.

Migratory functionalization of unactivated alkyl bromides for construction of all-carbon quaternary centers via transposed tert-C-radicals.

Despite remarkable recent advances in transition-metal-catalyzed C(sp)-C cross-coupling reactions, there remain challenging bond formations. One class of such reactions include the formation of tertiary-C(sp)-C bonds, presumably due to unfavorable steric interactions and competing isomerizations of tertiary alkyl metal intermediates. Reported herein is a Ni-catalyzed migratory 3,3-difluoroallylation of unactivated alkyl bromides at remote tertiary centers.

Selective C-F bond carboxylation of -difluoroalkenes with CO by photoredox/palladium dual catalysis.

The catalytic C-F bond carboxylation of organofluorines with CO gas remains a challenging problem in synthetic chemistry. Here, we describe a selective defluorinative carboxylation of -difluoroalkenes through photoredox/palladium dual catalysis. The C-F bond activation is enabled by single electron reduction through photoredox catalysis to generate a fluorovinyl radical, which subsequently participates in an unprecedented palladium-catalyzed carboxylation.

Which properties of the visual stimuli predict the type of representation used in mental rotation?

Two modes of internal representation, holistic and piecemeal transformation, have been reported as a means to perform mental rotation (MR) tasks. The stimulus complexity effect has been proposed as an indicator to disentangle between these two representation types. However, the complexity effect has not been fully confirmed owing to the fact that different performances could result from different types of stimuli.

Ni-catalyzed migratory fluoro-alkenylation of unactivated alkyl bromides with -difluoroalkenes.

We describe a nickel-catalyzed highly regio- and stereoselective migratory fluoro-alkenylation of unactivated alkyl bromides. A unique catalytic cycle merging alkyl nickel chain-walking and defluorinative coupling enables the introduction of a broad array of fluoroalkenyl moieties into carbon chains. Control experiments with other halogenated alkenes demonstrated the essential role of fluorine atoms in this reaction.

Intermolecular Carboamination of Unactivated Alkenes.

Herein, we report the first example of group transfer radical addition of O-vinylhydroxylamine derivatives onto unactivated alkenes. By utilizing O-vinylhydroxylamine derivatives as both the N- and C-donors, this reaction enables intermolecular carboamination of unactivated alkenes in an atom economical fashion. As the process is initiated through N-radical addition followed by C-transfer, linear carboamination products are afforded.

Rh-Catalyzed C-H bond alkylation of indoles with α,α-difluorovinyl tosylate via indolyl group migration.

Herein we demonstrate that an alkylation of indoles could be accessed through C-H bond functionalization with α,α-difluorovinyl tosylate. The key aspect for the effective alkylation is the influence of the fluorine substituents on the reactivity of the C[double bond, length as m-dash]C double bond, allowing regioselective insertion as well as an indolyl group shift process. Furthermore, the fluorides are removed through alcoholysis to furnish the alkylation product as a traceless auxiliary.

Nonconventional difluoroalkylation of C(sp)-H bonds through hydroarylation.

An unprecedented Rh-catalyzed C2-difluoroalkylation of indole derivatives with 2,2-difluorovinyl arenesulfonates has been reported. This reaction provides a rare instance of catalytic difluoroalkylation through hydroarylation of gem-difluoroalkenes. The sulfonate group works as a chelating ligand, thus stabilizing the rhodacycle intermediate, leading to the uncommon transformation.

Manganese-catalyzed synthesis of monofluoroalkenes via C-H activation and C-F cleavage.

The manganese-catalyzed α-fluoroalkenylation of arenes via C-H activation and C-F cleavage has been described. This protocol provides a very useful method for the synthesis of monofluoroalkenes with predominant unconventional E-isomer selectivity which complements the existing strategies for the access to these molecular architectures. In addition, the selectivity of β-defluorination in the catalytic cycle not only determines the configurations of the products but also obviates the use of external oxidants, providing a good example in the exploitation of manganese-catalyzed redox-neutral C-H transformations.

Metallic reductant-free synthesis of α-substituted propionic acid derivatives through hydrocarboxylation of alkenes with a formate salt.

A PGeP-pincer palladium-catalyzed hydrocarboxylation of styrenes to obtain pharmaceutically important α-arylpropionic acid derivatives was achieved using a formate salt as both a reductant and a CO source. The reaction was also applicable to vinylsulfone and acrylates. Isotope labeling experiments demonstrated that a CO-recycling mechanism is operative through generation and reaction of a benzylpalladium complex as a carbon nucleophile.

Pd/Cu cooperative catalysis: an efficient synthesis of (3-isoindazolyl)allenes via cross-coupling of 2-alkynyl azobenzenes and terminal alkynes.

An efficient synthesis of (3-isoindazolyl)allenes from 2-alkynyl azobenzenes and terminal alkynes via cooperative Pd(PPh)Cl/CuI-catalyzed cross-coupling has been developed. By making use of this approach, (3-isoindazolyl)allenes with various substituents can be synthesized in good to excellent yields. A rapid synthesis of biologically active indazolo[2,3-a]quinoline was also achieved using this method as the key step.

A Greedy Scanning Data Collection Strategy for Large-Scale Wireless Sensor Networks with a Mobile Sink.

Mobile sink is widely used for data collection in wireless sensor networks. It can avoid 'hot spot' problems but energy consumption caused by multihop transmission is still inefficient in real-time application scenarios. In this paper, a greedy scanning data collection strategy (GSDCS) is proposed, and we focus on how to reduce routing energy consumption by shortening total length of routing paths.

Characterization of a novel single-stranded RNA virus, closely related to fusariviruses, infecting the plant pathogenic fungus Alternaria brassicicola.

The alternaria blackspot of rapeseed is one of the most prominent diseases of rapeseed. It is caused by three species of the genus Alternaria: Alternaria brassicicola, Alternaria brassicae, and Alternaria raphanin. Here we report a novel positive-sense RNA virus from an A.

Use of formate salts as a hydride and a co2 source in PGeP-palladium complex-catalyzed hydrocarboxylation of allenes.

Use of formate salts as a hydride as well as a CO2 source was achieved in a PGeP-palladium complex-catalyzed hydrocarboxylation of allenes through a highly efficient decarboxylation-carboxylation process. This reaction proceeds under mild conditions and provides an alternative strategy for utilizing formate salts as a C1 source.

LPTA: location predictive and time adaptive data gathering scheme with mobile sink for wireless sensor networks.

This paper exploits sink mobility to prolong the lifetime of sensor networks while maintaining the data transmission delay relatively low. A location predictive and time adaptive data gathering scheme is proposed. In this paper, we introduce a sink location prediction principle based on loose time synchronization and deduce the time-location formulas of the mobile sink.

Adenosine A2A receptor antagonist istradefylline 20 versus 40 mg/day as augmentation for Parkinson's disease: a meta-analysis.

Background: Adenosine A2A receptor antagonist istradefylline 20 mg/day has been approved this year for manufacturing and market in Japan. Therefore, we did this meta-analysis to systematically evaluate the clinical applicability of 40 mg/day as augmentation to levodopa in patients with Parkinson's disease (PD).

Method: Randomized controlled trials (RCT) that compared istradefylline with placebo for short-course treatment of PD in adults were systematically reviewed up to November 2013.

Serum levels of tissue inhibitor of metalloproteinase-1 are correlated with liver fibrosis in patients with chronic hepatitis B.

Objective: To investigate the relationship between tissue inhibitor of metalloproteinase-1 (TIMP-1) expression and the severity of liver fibrosis in chronic hepatitis B (CHB) patients, and to explore the diagnostic value of serum TIMP-1.

Methods: A total of 159 CHB patients underwent liver biopsy for the analysis of liver fibrosis stages and inflammation. Serum TIMP-1 was determined by ELISA.

Transition-metal-free borylation of aryltriazene mediated by BF3·OEt2.

A practical and simple method for deaminoborylation of aryltriazene with bis(pinacolato)diboron has been developed that is mediated by BF(3)·OEt(2). Various arylboronic esters are prepared in moderate to good yields with this facile transition-metal-free procedure.

Dilator method and needle method for atrial transseptal puncture: a retrospective study from a cohort of 4443 patients.

Aims: To compare the safety and efficacy of a new dilator method vs the traditional needle method for transseptal puncture (TSP) in a large cohort study.

Methods And Results: From February 1995 to December 2010, 4443 consecutive patients undergoing TSP done either by a needle method or by a new dilator method were reviewed retrospectively. Data as procedure-related time and complications were evaluated.

Stereoselective plasma protein binding and target tissue distribution of clausenamide enantiomers in rats.

Stereoselective differences in pharmacokinetics between clausenamide (CLA) enantiomers have been found after intravenous and oral administration of each enantiomer to rats. The differences could be associated with protein binding of CLA enantiomers. By equilibrium dialysis methods, the binding of CLA enantiomers to rat plasma protein was investigated.