Metal-Ligand Cooperativity in MnI -Catalysed N-Formylation of Secondary Amides and Lactams Using CO2 at Room Temperature.

A MnI catalyst featuring redox-active tridentate phenalenyl (PLY) ligand has been used for catalytic N-formylation of secondary amides and lactams under 1 atm CO2 as a C1 source at room temperature for the first time. The protocol is applicable to a wide range of secondary amides including heterocycles, bio-active cinnamide derivatives and the diversification of therapeutic molecules. In-depth mechanistic investigations based on experimental outcomes and DFT calculations suggested an unconventional metal-ligand cooperation, where a ligand-centred radical plays a crucial role in initiating the reaction process.

Reduced-Phenalenyl-Based Molecule as a Super Electron Donor for Radical-Mediated C-N Coupling Catalysis at Room Temperature.

We demonstrate that an in situ generated di-reduced phenalenyl (PLY) species accumulates sufficiently high energy and acts as a super electron donor to generate aryl radicals from aryl halides to accomplish Buchwald-Hartwig-type C-N cross-coupling reactions at room temperature. This catalytic protocol does not require any external stimuli such as heat, light, or cathodic current. This protocol shows a wide variety of substrate scope covering different genres of aryl and heteroaryl halides with various aromatic as well as aliphatic amines and late-stage functionalization of the well-known natural products. The control experiments, along with extensive density functional theory (DFT) calculations, unveil that the aryl radical is generated by a single electron transfer from the di-reduced PLY to the aryl halide substrate. The aryl radical acts as an electrophile and binds with amine, leading to the chemically driven radical-mediated C-N cross-coupling under transition-metal-free conditions.

Supercritical carbon dioxide extracts of small cardamom and yellow mustard seeds have fasting hypoglycaemic effects: diabetic rat, predictive iHOMA2 models and molecular docking study.

In the present investigation, the supercritical carbon dioxide (SC-CO2) extracts of small cardamom (SC) and yellow mustard (YM) seeds have been investigated for their efficacies in combating type 2 diabetes in streptozotocin-induced Wistar albino rats. Fasting blood glucose (FBG) levels in the rats were monitored on days 8, 15 and 21. On day 15, FBG level reduced appreciably by 31·49 % in rats treated with SC seed extract and by 32·28 % in rats treated with YM seed extract, comparable to metformin (30·70 %) and BGR-34 (a commercial polyherbal drug) (31·81 %) administered rats. Either extract exhibited desirable effects on hepatic glucose-6-phosphatase, glucose-6-phosphate dehydrogenase (G6PD) and catalase activities in controlling diabetes. A molecular docking exercise was conducted to identify specific compounds in the extracts which possessed augmenting effect on G6PD. The results revealed that all the bioactive compounds in the extracts have binding affinities with the enzyme and contributed to the antidiabetic efficacies of the extracts as G6PD augmenters. The effects of the extracts on insulin sensitivity and glucose uptake were investigated using non-invasive modelling by iHOMA2 software. This in vitro approach indicated that extract administration resulted in increased both insulin sensitivity of the liver and glucose uptake in the gut. The findings of the present study attest these SC-CO2 extracts of the spices as safe alternatives of metformin and BGR-34 in combating type 2 diabetes and could be safely subjected to clinical studies. These extracts could also be employed in designing proactive food supplements in mitigating the metabolic disorder.

Ultrasonication-assisted extraction of a phytomelatonin-rich, erucic acid-lean nutraceutical supplement from mustard seeds: an antioxidant synergy in the extract by reductionism.

Phytomelatonin-rich (194.02 ± 2.45-205.80 ± 1.67 ng/g of dry mustard seeds) and erucic acid-lean (below 2%) extracts from an oilseed crop, (yellow and black mustard seeds) have been successfully obtained by ultrasonication-assisted-extraction in ethanol-water. Fourier-transform infrared spectroscopy and liquid chromatography-mass spectrum analyses have confirmed the presence of phytomelatonin along with tocopherol, ascorbic acid, limonene and linalool in the extract. Field emission scanning electron micrographs confirmed the cavitational effects of sonication on mustard seed matrices. Electron paramagnetic resonance spectroscopy established the strong antioxidant activities (72.25-75.49%) of the extracts foregoing erroneous spectrophotometric result of pan assay interference compounds. A synergistic effect value of 1.13 (greater than unity) confirmed synergistic co-existence of the antioxidants in the extract. This study interestingly revealed that an antioxidant synergy could be obtained by classical reductionism. Acute oral toxicity of the extracts were found to be greater than 5000 mg/kg body weight of rats. The extracts are perfectly safe to be utilized as antioxidative food supplements.

Integrating Organic Lewis Acid and Redox Catalysis: The Phenalenyl Cation in Dual Role.

In recent years, merging different types of catalysis in a single pot has drawn considerable attention and these catalytic processes have mainly relied upon metals. However, development of a completely metal free approach integrating organic redox and organic Lewis acidic property into a single system has been missing in the current literature. This study establishes that a redox active phenalenyl cation can activate one of the substrates by single electron transfer process while the same can activate the other substrate by a donor-acceptor type interaction using its Lewis acidity. This approach has successfully achieved light and metal-free catalytic C-H functionalization of unactivated arenes at ambient temperature (39 entries, including core moiety of a top-selling molecule boscalid), an economically attractive alternative to the rare metal-based multicatalysts process. A tandem approach involving trapping of reaction intermediates, spectroscopy along with density functional theory calculations unravels the dual role of phenalenyl cation.

An Iron-Based Long-Lived Catalyst for Direct C-H Arylation of Arenes and Heteroarenes.

Direct C-H arylation of arenes and heteroarenes to biaryls at ambient temperature has been accomplished using a phenalenyl-supported iron(III) catalyst. The present catalyst requires a chemical reductant such as potassium and functions without any light stimulation. C-H arylation of various heteroarenes including pyridine as well as unactivated arene such as benzene delivered good to excellent yield (28 examples, up to 92 %) at room temperature. A combined effort based on experiments and theoretical calculations established that a phenalenyl-based radical species (generated by chemical reduction of the iron(III) coordinated phenalenyl complex) plays key role during the catalysis. Furthermore, this catalyst displayed remarkable stability during the catalysis, as evident from the fact that it was still usable over ten consecutive catalytic runs without losing its catalytic efficiency.

A 46-year-old woman presenting with anterior mediastinal mass and superior vena cava obstruction syndrome.

Mucormycosis can rarely lead to an anterior mediastinal mass and a high index of suspicion is necessary so that intervention can be carried out at an early stage. https://bit.ly/4aUuqvc.

Dietary Polyphenols: Review on Chemistry/Sources, Bioavailability/Metabolism, Antioxidant Effects, and Their Role in Disease Management.

Polyphenols, as secondary metabolites ubiquitous in plant sources, have emerged as pivotal bioactive compounds with far-reaching implications for human health. Plant polyphenols exhibit direct or indirect associations with biomolecules capable of modulating diverse physiological pathways. Due to their inherent abundance and structural diversity, polyphenols have garnered substantial attention from both the scientific and clinical communities. The review begins by providing an in-depth analysis of the chemical intricacies of polyphenols, shedding light on their structural diversity and the implications of such diversity on their biological activities. Subsequently, an exploration of the dietary origins of polyphenols elucidates the natural plant-based sources that contribute to their global availability. The discussion extends to the bioavailability and metabolism of polyphenols within the human body, unraveling the complex journey from ingestion to systemic effects. A central focus of the review is dedicated to unravelling the antioxidant effects of polyphenols, highlighting their role in combating oxidative stress and associated health conditions. The comprehensive analysis encompasses their impact on diverse health concerns such as hypertension, allergies, aging, and chronic diseases like heart stroke and diabetes. Insights into the global beneficial effects of polyphenols further underscore their potential as preventive and therapeutic agents. This review article critically examines the multifaceted aspects of dietary polyphenols, encompassing their chemistry, dietary origins, bioavailability/metabolism dynamics, and profound antioxidant effects. The synthesis of information presented herein aims to provide a valuable resource for researchers, clinicians, and health enthusiasts, fostering a deeper understanding of the intricate relationship between polyphenols and human health.

Abnormal N-heterocyclic Carbene Based Ni(II) π-allyl Complex towards Molecular Oxygen Activation.

Abnormal N-heterocyclic carbene (aNHC) based Ni(II) π-allyl complexes (3 and 4) were synthesized starting from a Ni(0) precursor. These complexes were characterized by NMR spectroscopy, single-crystal X-ray crystallography (4) and elemental analysis data. The underlying mechanism for the formation of Ni(II) η3 -allyl complexes from a Ni(0) precursor on treatment with a free abnormal N-heterocyclic carbene in absence of any external additive or oxidant was unraveled. Later, complex 3 was exposed to O2 gas under ambient pressure resulting in molecular oxygen activation to form a µ-hydroxo bridged Ni(II) dimer.

Redox-active ligand based Mn(I)-catalyst for hydrosilylative ester reduction.

Herein a Mn(I) catalyst bearing a redox-active phenalenyl (PLY) based ligand is reported for the efficient hydrosilylation of esters to alcohols using the inexpensive silane source polymethylhydrosiloxane (PMHS) under mild conditions. Mechanistic investigations suggest a strong ligand-metal cooperation where a ligand-based single electron transfer (SET) process initiates the reaction through Si-H bond activation.

Correction: Redox-active ligand based Mn(I)-catalyst for hydrosilylative ester reduction.

Correction for 'Redox-active ligand based Mn(I)-catalyst for hydrosilylative ester reduction' by Soumi Chakraborty et al., Chem. Commun., 2021, 57, 12671-12674, DOI: 10.1039/D1CC05614J.

Designing a Cr-catalyst bearing redox non-innocent phenalenyl-based ligand towards hydrosilylative CO2 functionalization.

Herein, we report the synthesis of a Cr(iii)-complex bearing a redox non-innocent phenalenyl-based ligand and its use as a catalyst for SET mediated hydrosilylative reduction of carbon dioxide towards formylation of primary amides under mild conditions. A preliminary mechanistic picture for this transformation has been proposed by isolation and characterization of several reactive intermediates.

Consortia of bioactives in supercritical carbon dioxide extracts of mustard and small cardamom seeds lower serum cholesterol levels in rats: new leads for hypocholesterolaemic supplements from spices.

Melatonin-rich and 1,8-cineole-rich extracts have been successfully obtained from yellow mustard (YM) and small cardamom (SC) seeds, respectively, employing green technology of supercritical CO2 (SC-CO2) extraction. Chemical profiling confirmed the presence of melatonin and 1,8-cineole and co-extractants in the respective extracts. Electron paramagnetic resonance spectroscopy attested strong antioxidant activities of the extracts foregoing pan-assay interference compounds involved in spectroscopic analysis. These extracts also exhibited synergistic efficacies greater than unity confirming antioxidant synergy among the co-extracted bioactives therein. To ascertain hypocholesterolaemic efficacies, these extracts were co-administered orally with Triton X (at the pre-optimised dose of 175 mg/kg body weight (BW)) to Wistar albino rats at doses of 550, 175 and 55 mg/kg BW. Serum total cholesterol levels in the rats were monitored on days 3, 7, 15 and 21. On day 21, total cholesterol level reduced appreciably by 49·44 % in rats treated with YM seed extract and by 48·95 % in rats treated with SC seed extract, comparable with atorvastatin-administered rats (51·09 %). Either extract demonstrated inhibitory effects on hepatic 3-hydroxy-3-methyl-glutaryl-CoA (HMG-CoA) reductase activity. A molecular docking exercise identified specific compounds in the extracts which possessed binding affinities comparable with therapeutically used HMG-CoA reductase inhibitors. In silico and in vivo studies concertedly concluded that the consortium of bioactive components in the extracts cannot be considered as invalid metabolic panaceas and therefore these 'green' extracts could be safely subjected to clinical studies as preventive biotherapeutics for hypercholesterolaemia. These extracts could be consumed per se as hypocholesterolaemic supplements or could be ingredients of new spice-based therapeutic foods.