Harnessing Multi-Center-2-Electron Bonds for Carbene Metal-Hydride Nanocluster Catalysis.

N-Heterocyclic carbene (NHC) ligands possess the ability to stabilize metal-based nanomaterials for a broad range of applications. With respect to metal-hydride nanomaterials, however, carbenes are rare, which is surprising if one considers the importance of metal-hydride bonds across the chemical sciences. In this study, we introduce a bottom-up approach leveraging preexisting metal-metal m-center-n-electron (mc-ne) bonds to access a highly stable cyclic(alkyl)amino carbene (CAAC) copper-hydride nanocluster, [(CAAC)6Cu14H12][OTf]2 with superior stability compared to Stryker's reagent, a popular commercial phosphine-based copper hydride catalyst.

Tungsten-catalyzed stereodivergent isomerization of terminal olefins.

Catalytic alkene isomerization is a powerful synthetic strategy for preparing valuable internal alkenes from simple feedstocks. The utility of olefin isomerization hinges on the ability to control both positional and stereoisomerism to access a single product among numerous potential isomers. Within base-metal catalysis, relatively little is known about how to modulate reactivity and selectivity with group 6 metal-catalyzed isomerization.

Palladium Bisphosphine Monoxide Complexes: Synthesis, Scope, Mechanism, and Catalytic Relevance.

Recent studies in transition metal catalysis employing chelating phosphines have suggested a role for partial ligand oxidation in formation of the catalytically active species, with potentially widespread relevance in a number of catalytic systems. We examine the internal redox reaction of Pd(bisphosphine)X (X = Cl, OAc, ) complexes to reveal previously underexplored aspects of bisphosphine monoxides (BPMOs), including evaluation of ligand structure and development of general reaction conditions to access a collection of structurally diverse BPMO precatalysts based on organopalladium oxidative addition complexes. In particular, a series of Pd(BPMO)(R)(X) (R = aryl, alkyl; X = I, Br) oxidative addition complexes bearing 24 different BPMO ligands were characterized by NMR and X-ray crystallography.

Digital Coaching to Address Health, Wellness, and Burnout Among Healthcare Workers: Pilot Study Results.

Background: Healthcare worker (HCW) well-being is essential for safe, high-quality patient care, but clinicians and front-line staff continue to experience alarming rates of burnout. This pilot study evaluated a novel 6-week program of remote wellness coaching supported by daily digital messaging to reduce burnout and increase well-being among HCWs.

Methods: In spring 2023, staff from a large community health center in California were invited to participate in this single-group pretest-posttest study in an academic-practice partnership.

Hemilabile and Redox-Active Quinone Ligands Unlock sp-Rich Couplings in Nickel-Catalyzed Olefin Carbosulfenylation.

A three-component coupling approach toward structurally complex dialkylsulfides is described via the nickel-catalyzed 1,2-carbosulfenylation of unactivated alkenes with organoboron nucleophiles and alkylsulfenamide (N-S) electrophiles. Efficient catalytic turnover is facilitated using a tailored N-S electrophile containing an N-methyl methanesulfonamide leaving group, allowing catalyst loadings as low as 1 mol %. Regioselectivity is controlled by a collection of monodentate, weakly coordinating native directing groups, including sulfonamides, amides, sulfinamides, phosphoramides, and carbamates.

-selective Cyclopropanation of Nonconjugated Alkenes with Diverse Pronucleophiles via Directed Nucleopalladation.

A facile approach to obtaining densely functionalized cyclopropanes is described. The reaction proceeds under mild conditions via the directed nucleopalladation of nonconjugated alkenes with readily available pronucleophiles and gives excellent yields and good -selectivity using I and TBHP as oxidants. Pronucleophiles bearing a diverse collection of electron-withdrawing groups, including -CN, -COR, -COR, -SOPh, -CONHR, and -NO, are well tolerated.

Diversification of Pharmaceutical Manufacturing Processes: Taking the Plunge into the Non-PGM Catalyst Pool.

Recent global events have led to the cost of platinum group metals (PGMs) reaching unprecedented heights. Many chemical companies are therefore starting to seriously consider and evaluate if and where they can substitute PGMs for non-PGMs in their catalytic processes. This review covers recent highly relevant applications of non-PGM catalysts in the modern pharmaceutical industry.

Tackling multi-drug resistant fungi by efflux pump inhibitors.

The emergence of multidrug-resistant fungi is of grave concern, and its infections are responsible for significant deaths among immunocompromised patients. The treatment of fungal infections primarily relies on a clinical class of antibiotics, including azoles, polyenes, echinocandins, polyketides, and a nucleotide analogue. However, the incidence of fungal infections is increasing as the treatment for human and plant fungal infections overlaps with antifungal drugs.

Stereodivergent, Kinetically Controlled Isomerization of Terminal Alkenes via Nickel Catalysis.

Because internal alkenes are more challenging synthetic targets than terminal alkenes, metal-catalyzed olefin mono-transposition (i.e., positional isomerization) approaches have emerged to afford valuable E- or Z- internal alkenes from their complementary terminal alkene feedstocks.

Targeting epidermal growth factor receptor and its downstream signaling pathways by natural products: A mechanistic insight.

The epidermal growth factor receptor (EGFR) is a transmembrane receptor tyrosine kinase (RTK) that maintains normal tissues and cell signaling pathways. EGFR is overactivated and overexpressed in many malignancies, including breast, lung, pancreatic, and kidney. Further, the EGFR gene mutations and protein overexpression activate downstream signaling pathways in cancerous cells, stimulating the growth, survival, resistance to apoptosis, and progression of tumors.

Benchtop Nickel Catalysis Invigorated by Electron-Deficient Diene Ligands.

ConspectusDue to the rarity of precious metals like palladium, nickel catalysis is becoming an increasingly important player in organic synthesis, especially for the formation of bonds with sp-hybridized carbon centers. Traditionally, catalytic processes involving active Ni(0) species have relied on Ni(COD) or in situ reduction of Ni(II) salts. However, Ni(COD) is an air- and temperature-sensitive material that requires use in an inert-atmosphere glovebox, and in situ reduction protocols of Ni(II) salts using metallic or organometallic reductants add additional complications to reaction development.

Nickel-Electrocatalytic Decarboxylative Arylation to Access Quaternary Centers.

There is a pressing need, particularly in the field of drug discovery, for general methods that will enable direct coupling of tertiary alkyl fragments to (hetero)aryl halides. Herein a uniquely powerful and simple set of conditions for achieving this transformation with unparalleled generality and chemoselectivity is disclosed. This new protocol is placed in context with other recently reported methods, applied to simplify the routes of known bioactive building blocks molecules, and scaled up in both batch and flow.

Electroreductive Synthesis of Nickel(0) Complexes.

Over the last fifty years, the use of nickel catalysts for facilitating organic transformations has skyrocketed. Nickel(0) sources act as useful precatalysts because they can enter a catalytic cycle through ligand exchange, without needing to undergo additional elementary steps. However, most Ni(0) precatalysts are synthesized with stoichiometric aluminum-hydride reductants, pyrophoric reagents that are not atom-economical and must be used at cryogenic temperatures.

Ligand-Enabled Carboamidation of Unactivated Alkenes through Enhanced Organonickel Electrophilicity.

Catalytic carboamination of alkenes is a powerful synthetic tool to access valuable amine scaffolds from abundant and readily available alkenes. Although a number of synthetic approaches have been developed to achieve the rapid buildup of molecular complexity in this realm, the installation of diverse carbon and nitrogen functionalities onto unactivated alkenes remains underdeveloped. Here we present a ligand design approach to enable nickel-catalyzed three-component carboamidation that is applicable to a wide range of alkenyl amine derivatives via a tandem process involving alkyl migratory insertion and inner-sphere metal-nitrenoid transfer.

Brief peer coaching complements daily digital messages for chronic disease prevention among young adult Latinas.

Young Latinas face multiple health challenges that place them at high risk for chronic diseases. Digital health promotion interventions can offer education and support to activate self-care and preventive behaviors. This pilot study evaluated a brief, theory-informed, culturally tailored intervention, Examen Tu Salud, that provided daily text and multimedia messages and weekly peer coaching via videoconference to improve health behaviors among young adult Latina women.

Natural products acting against through membrane and cell wall disruption.

Covering: 2015 to 2022 () is responsible for several community and hospital-acquired infections with life-threatening complications such as bacteraemia, endocarditis, meningitis, liver abscess, and spinal cord epidural abscess. In recent decades, the abuse and misuse of antibiotics in humans, animals, plants, and fungi and the treatment of nonmicrobial diseases have led to the rapid emergence of multidrug-resistant pathogens. The bacterial wall is a complex structure consisting of the cell membrane, peptidoglycan cell wall, and various associated polymers.

Catalytic σ-Bond Annulation with Ambiphilic Organohalides Enabled by β-X Elimination.

We describe a catalytic cascade sequence involving directed C(sp )-H activation followed by β-heteroatom elimination to generate a Pd (π-alkene) intermediate that then undergoes redox-neutral annulation with an ambiphilic aryl halide to access 5- and 6-membered (hetero)cycles. Various alkyl C(sp )-oxygen, nitrogen, and sulfur bonds can be selectively activated, and the annulation proceeds with high diastereoselectivity. The method enables modification of amino acids with good retention of enantiomeric excess, as well as σ-bond ring-opening/ring-closing transfiguration of low-strain heterocycles.

High engagement in nonpharmaceutical interventions and their associations with reduced COVID-19 among US college students.

Background: Nonpharmaceutical interventions, including face mask-wearing, physical distancing, and avoidance of crowds and poorly ventilated spaces, have been widely recommended to limit the spread of SARS-CoV-2. To date, there is little data available on engagement in nonpharmaceutical interventions and COVID-19 in college students. Using a large sample of college students, we estimate the prevalence of engagement in mask-wearing, physical distancing, and avoidance of crowds/poorly ventilated spaces and their associations with COVID-19.

Redox-Paired Alkene Difunctionalization Enables Skeletally Divergent Synthesis.

Multistep organic synthesis enables conversion of simple chemical feedstocks into a more structurally complex product that serves a particular function. The target compound is forged over several steps, with concomitant generation of byproducts in each step to account for underlying mechanistic features of the reactions (e.g.

(CAAC)Copper Catalysis Enables Regioselective Three-Component Carboboration of Terminal Alkynes.

Cyclic(alkyl)(amino)carbene (CAAC) ligands are found to perturb regioselectivity of the copper-catalyzed carboboration of terminal alkynes, favoring the less commonly observed internal alkenylboron regiosomer through an α-selective borylcupration step. A variety of carbon electrophiles participate in the reaction, including allyl alcohols derivatives and alkyl halides. The method provides a straightforward and selective route to versatile tri-substituted alkenylboron compounds that are otherwise challenging to access.

Enantioselective Hydroalkenylation and Hydroalkynylation of Alkenes Enabled by a Transient Directing Group: Catalyst Generality through Rigidification.

The catalytic enantioselective synthesis of α-chiral alkenes and alkynes represents a powerful strategy for rapid generation of molecular complexity. Herein, we report a transient directing group (TDG) strategy to facilitate site-selective palladium-catalyzed reductive Heck-type hydroalkenylation and hydroalkynylation of alkenylaldehyes using alkenyl and alkynyl bromides, respectively, allowing for construction of a stereocenter at the δ-position with respect to the aldehyde. Computational studies reveal the dual beneficial roles of rigid TDGs, such as L-tert-leucine, in promoting TDG binding and inducing high levels of enantioselectivity in alkene insertion with a variety of migrating groups.

Glucometrics: Where Are We Now?

Purpose Of Review: Inpatient glucose data analysis, or glucometrics, has developed alongside the growing emphasis on glycemic control in the hospital. Shortcomings in the initial capabilities for glucometrics have pushed advancements in defining meaningful units of measurement and methods for capturing glucose data. This review addresses the growth in glucometrics and ends with its promising new state.

Revised Mechanism of C(sp)-C(sp) Reductive Elimination from Ni(II) with the Assistance of a Z-Type Metalloligand.

Reductive elimination is a key step in Ni-catalyzed cross-couplings. Compared with processes that proceed from Ni(III) or Ni(IV) intermediates, C(sp)-C(sp) reductive eliminations from Ni(II) centers are challenging due to the weak oxidizing ability of Ni(II) species. In this report, we present computational evidence that supports a mechanism in which Zn coordination to the nickel center as a Z-type ligand accelerates reductive elimination.

Liberals are Believers: Young People Assign Trust to Social Media for COVID-19 Information.

The COVID-19 pandemic has challenged existing health communication strategies as more people turn to social media as a primary health information source. Although many studies have explored how young people use social media, this study examined how sociodemographic factors and political ideology are associated with use and trust in social media as a source for COVID-19 information among young adults, and how use and trust in social media as a COVID-19 information source are associated with their beliefs about COVID-19. In Spring 2021, an online survey was conducted among 2,105 18-29-year-old students at an urban university in California.

COVID-19 vaccine coverage among college students following vaccine mandates.

Objective: Colleges are potential hotspots for transmission of SARS-CoV-2 due to lower immunization rates and possible close contacts among young adults. Some universities have implemented policies mandating COVID-19 vaccination; however, their effects remain uncertain. We estimated COVID-19 vaccination rates with and without university-mandated vaccination policies.