(Phenoxyimine)nickel-Catalyzed C(sp2)-C(sp3) Suzuki-Miyaura Cross-Coupling: Evidence for a Recovering Radical Chain Mechanism.

Phenoxyimine (FI)-nickel(II)(2-tolyl)(DMAP) compounds were synthesized and evaluated as precatalysts for the C(sp2)-C(sp3) Suzuki-Miyaura cross coupling of (hetero)arylboronic acids with alkyl bromides. With 5 mol % of the optimal (MeOMeFI)Ni(Aryl)(DMAP) precatalyst, the scope of the cross-coupling reaction was established and included a variety of (hetero)arylboronic acids and alkyl bromides (>50 examples, 33-97% yield). A ß-hydride elimination-reductive elimination sequence from reaction with potassium isopropoxide base, yielding a potassium (FI)nickel(0)ate, was identified as a catalyst activation pathway that is responsible for halogen atom abstraction from the alkyl bromide. A combination of NMR and EPR spectroscopies identified (FI)nickel(II)-aryl complexes as the resting state during catalysis with no evidence for long-lived organic radical or odd-electron nickel intermediates. These data establish that the radical chain is short-lived and undergoes facile termination and also support a "recovering radical chain" process whereby the (FI)nickel(II)-aryl compound continually (re)initiates the radical chain. Kinetic studies established that the rate of C(sp2)-C(sp3) product formation was proportional to the concentration of the (FI)nickel(II)-aryl resting state that captures the alkyl radical for chain propagation. The proposed mechanism involves two key and concurrently operating catalytic cycles; the first involving a nickel(I/II/III) radical propagation cycle consisting of radical capture at (FI)nickel(II)-aryl, C(sp2)-C(sp3) reductive elimination, bromine atom abstraction from C(sp3)-Br, and transmetalation; and the second involving an off-cycle catalyst recovery process by slow (FI)nickel(II)-aryl → (FI)nickel(0)ate conversion for nickel(I) regeneration.

Phenoxythiazoline (FTz)-Cobalt(II) Precatalysts Enable C(sp2 )-C(sp3 ) Bond-Formation for Key Intermediates in the Synthesis of Toll-like Receptor 7/8 Antagonists.

Evaluation of the relative rates of the cobalt-catalyzed C(sp2 )-C(sp3 ) Suzuki-Miyaura cross-coupling between the neopentylglycol ester of 4-fluorophenylboronic acid and N-Boc-4-bromopiperidine established that smaller N-alkyl substituents on the phenoxyimine (FI) supporting ligand accelerated the overall rate of the reaction. This trend inspired the design of optimal cobalt catalysts with phenoxyoxazoline (FOx) and phenoxythiazoline (FTz) ligands. An air-stable cobalt(II) precatalyst, (FTz)CoBr(py)3 was synthesized and applied to the cross-coupling of an indole-5-boronic ester nucleophile with a piperidine-4-bromide electrophile that is relevant to the synthesis of reported toll-like receptor (TLR) 7/8 antagonist molecules including afimetoran. Addition of excess KOMe⋅B(Oi Pr)3 improved catalyst lifetime due to attenuation of alkoxide basicity that otherwise resulted in demetallation of the FI chelate. A first-order dependence on the cobalt precatalyst and a saturation regime in nucleophile were observed, supporting turnover-limiting transmetalation and the origin of the observed trends in N-imine substitution.

Gender Differences in the Association between Workplace Bullying and Depression among Korean Employees.

Workplace bullying is a prevalent issue with a significant impact on employees' mental health. This study aimed to explore the relationship between workplace bullying and the prevalence of depression, with a particular focus on the role of gender. A total of 12,344 Korean employees aged 19-65 years were included in the study. They completed the Center for Epidemiologic Studies Depression Scale (CES-D) and a score of 16 or higher in CES-D indicated depression. The association between workplace bullying and depression was analyzed using logistic regression analyses. The average CES-D scores were higher for both male and female employees who experienced bullying than for those who did not (p < 0.001). The association between the experience of workplace bullying and the prevalence of depression was statistically significant for both genders, with a stronger correlation observed among male employees (p for interaction < 0.001). Organizations are urged to address workplace bullying, particularly for male employees, through the implementation of anti-bullying strategies and policies, as well as the provision of mental health resources and support.

Surface modification of polypropylene hollow fiber membranes using fluorosilane for CO2 absorption in a gas-liquid membrane contactor.

Conventional methods for improving the hydrophobicity of polypropylene (PP) membranes to prevent wetting phenomena require complex pretreatment procedures in order to activate the surface for enabling the reaction with fluorosilane (FS)-based materials. This study successfully prepared PP membrane contactors with enhanced hydrophobicity through a simple single-step dip-coating method using perfluoroether-grafted silanes for CO2 capture. The FS coating layer on the PP membrane surface was confirmed through ATR-FTIR spectroscopy, XPS, FE-SEM, and EDS. Furthermore, the evaluation of the CO2 absorption performance and long-term stability of the FS-coated PP membrane according to the variation of the gas flow rate (50, 100, 200, 400, and 800 mL/min) confirmed the superior chemical stability and durability of our membranes to those of previously reported hydrophobic membranes. The as-prepared FS-coated PP membrane expands the application scope of gas-liquid membrane contactors for CO2 capture from the flue gas of coal-fired power plants.

Investigation of the C-N Bond-Forming Step in a Photoinduced, Copper-Catalyzed Enantioconvergent N-Alkylation: Characterization and Application of a Stabilized Organic Radical as a Mechanistic Probe.

Whereas photoinduced, copper-catalyzed couplings of nitrogen nucleophiles with alkyl electrophiles have recently been shown to provide an attractive approach to achieving a variety of enantioselective C-N bond constructions, mechanistic studies of these transformations have lagged the advances in reaction development. Herein we provide mechanistic insight into a previously reported photoinduced, copper-catalyzed enantioconvergent C-N coupling of a carbazole nucleophile with a racemic tertiary α-haloamide electrophile. Building on the isolation of a copper(II) model complex whose EPR parameters serve as a guide, we independently synthesize two key intermediates in the proposed catalytic cycle, a copper(II) metalloradical (L*CuII(carb')2) (L* = a monodentate chiral phosphine ligand; carb' = a carbazolide ligand), as well as a tertiary α-amide organic radical (R·); the generation and characterization of R· was guided by DFT calculations, which suggested that it would be stable to homocoupling. Continuous-wave (CW) and pulse EPR studies, along with corresponding DFT calculations, are among the techniques used to characterize these reactive radicals. We establish that these two radicals do indeed combine to furnish the C-N coupling product in good yield and with significant enantiomeric excess (77% yield, 55% ee), thereby supporting the chemical competence of these proposed intermediates. DFT calculations are consistent with R· initially binding to copper(II) via a dative interaction from the closed-shell carbonyl oxygen atom of the radical, which positions the α-carbon for direct reaction with the copper(II)-bound carbazole N atom, to generate the C-N bond with enantioselectivity, without the formation of an alkylcopper(III) intermediate.

Correlation Assisted Strong Uncorrelating Transform Complex Common Spatial Patterns for Spatially Distant Channel Data.

The Strong Uncorrelating Transform Complex Common Spatial Patterns (SUTCCSP) algorithm, designed for multichannel data analysis, has a limitation on keeping the correlation information among channels during the simultaneous diagonalization process of the covariance and pseudocovariance matrices. This paper focuses on the importance of preserving the correlation information among multichannel data and proposes the correlation assisted SUTCCSP (CASUT) algorithm to address this issue. The performance of the proposed algorithm was demonstrated by classifying the motor imagery electroencephalogram (EEG) dataset. The features were first extracted using CSP algorithms including the proposed method, and then the random forest classifier was utilized for the classification. Experiments using CASUT yielded an average classification accuracy of 78.10 (%), which significantly outperformed those of original CSP, Complex Common Spatial Patterns (CCSP), and SUTCCSP with p-values less than 0.01, tested by the Wilcoxon signed rank test.

Carbon-Fluorine Reductive Elimination from Nickel(III) Complexes.

We report a C-F reductive elimination from a characterized first-row aryl metal fluoride complex. Reductive elimination from the presented nickel(III) complexes is faster than C-F bond formation from any other characterized aryl metal fluoride complex.