eFluorination of Activated Alcohols Using Collidinium Tetrafluoroborate.

Tertiary C-F bonds are important structural designs; however, they suffer from challenging synthesis. Current methodologies use corrosive amine-HF salts or expensive and hazardous catalysts and reagents. Our group recently introduced collidinium tetrafluoroborate as an efficient fluorinating agent for anodic decarboxyfluorination reactions. Nevertheless, tertiary carboxylic acids are less readily available and more challenging to prepare than their alcohol analogues. Herein we report a practical, mild, and cheap electrochemical method to achieve deoxyfluorination of hindered carbon centers.

Exosomes in the Diagnosis and Treatment of Renal Cell Cancer.

Renal cell carcinoma (RCC) is the most prevalent type of kidney cancer originating from renal tubular epithelial cells, with clear cell RCC comprising approximately 80% of cases. The primary treatment modalities for RCC are surgery and targeted therapy, albeit with suboptimal efficacies. Despite progress in RCC research, significant challenges persist, including advanced distant metastasis, delayed diagnosis, and drug resistance. Growing evidence suggests that extracellular vesicles (EVs) play a pivotal role in multiple aspects of RCC, including tumorigenesis, metastasis, immune evasion, and drug response. These membrane-bound vesicles are released into the extracellular environment by nearly all cell types and are capable of transferring various bioactive molecules, including RNA, DNA, proteins, and lipids, aiding intercellular communication. The molecular cargo carried by EVs renders them an attractive resource for biomarker identification, while their multifarious role in the RCC offers opportunities for diagnosis and targeted interventions, including EV-based therapies. As the most versatile type of EVs, exosomes have attracted much attention as nanocarriers of biologicals, with multi-range signaling effects. Despite the growing interest in exosomes, there is currently no widely accepted consensus on their subtypes and properties. The emerging heterogeneity of exosomes presents both methodological challenges and exciting opportunities for diagnostic and clinical interventions. This article reviews the characteristics and functions of exosomes, with a particular reference to the recent advances in their application to the diagnosis and treatment of RCC.

Ageing perspective on cognitive outcomes from reproductive hormone adjustments.

In addition to primary reproductive functions, gonadal hormones play an important role in an array of neural mechanisms across the human lifespan. The ageing-related decline in their activity has been linked to the deterioration of cognitive functions in otherwise healthy women, associated with menopause transition, contributing to higher incidents of post-menopause dementia. Given the growing utility of gonadal steroids for birth control, as well as for compensatory treatment of menopause and oophorectomy symptoms, and adjuvant transgender therapy, their long-term effects on neural mechanisms warrant comprehensive assessment. In this article, we present an ageing perspective on the cognitive outcomes from contraceptive and replacement therapeutic use of gonadal hormones and discuss their effects on the risk of developing Alzheimer's and Parkinson's dementia. Despite rising data supporting the ameliorative effects of reproductive hormones on cognitive facilities, their impact varies depending on study design and type of intervention, thus, implying dynamic neuro-endocrine interactions with complex compensatory mechanisms. Elucidating differential effects of reproductive hormone adjustments on cognition with underlying mechanisms is expected not only to shed light on important aspects of brain ageing and dementia but to facilitate their use in personalized medicine with improved safety margins and therapeutic outcomes.

eHydrogenation: Hydrogen-free Electrochemical Hydrogenation.

Hydrogenation reactions are staple transformations commonly used across scientific fields to synthesise pharmaceuticals, natural products, and various functional materials. However, the vast majority of these reactions require the use of a toxic and costly catalyst leading to unpractical, hazardous and often functionally limited conditions. Herein, we report a new, general, practical, efficient, mild and high-yielding hydrogen-free electrochemical method for the reduction of alkene, alkyne, nitro and azido groups. Finally, this method has been applied to deuterium labelling.

eFluorination Using Cheap and Readily Available Tetrafluoroborate Salts.

A practical electrochemical method for the rapid, safer, and mild synthesis of tertiary hindered alkyl fluorides from carboxylic acids has been developed without the need for hydrofluoric acid salts or non-glass reactors. In this anodic fluorination, collidinium tetrafluoroborate acts as both the supporting electrolyte and fluoride donor. A wide range of functional groups has been shown to be compatible, and the possibility of scale-up using flow electrochemistry has also been demonstrated.

Electrochemical Isothiocyanation of Primary Amines.

Isothiocyanates are ubiquitous building blocks used across the fields. Nevertheless, their classical syntheses very often rely on the use of toxic and expensive reagents. Herein, we report a new practical, mild, high-yielding, and supporting-electrolyte-free electrochemical method for the preparation of aliphatic and aromatic isothiocyanates from amine and carbon disulfide.

A Palladium Iodide-Catalyzed Oxidative Aminocarbonylation-Heterocyclization Approach to Functionalized Benzimidazoimidazoles.

A novel carbonylative approach to the synthesis of functionalized 1H-benzo[d]imidazo[1,2-a]imidazoles is presented. The method consists of the oxidative aminocarbonylation of N-substituted-1-(prop-2-yn-1-yl)-1H-benzo[d]imidazol-2-amines, carried out in the presence of secondary nucleophilic amines, to give the corresponding alkynylamide intermediates, followed by in situ conjugated addition and double-bond isomerization, to give 2-(1-alkyl-1H-benzo[d]imidazo[1,2-a]imidazol-2-yl)acetamides. Products were obtained in good to excellent yields (64-96%) and high turnover numbers (192-288 mol of product per mol of catalyst) under relatively mild conditions (100 °C under 20 atm of a 4:1 mixture of CO-air), using a simple catalytic system, consisting of PdI2 (0.33 mol %) in conjunction with KI (0.33 equiv).