Versatile dehydrogenation of carbonyls enabled by an iodine(III) reagent.

We report the utilisation of an iodine(III) reagent to access α,β-unsaturated carbonyls from the corresponding silyl enol ethers of ketones and aldehydes, and from enol phosphates of lactones and lactams. The transformation is rapid, scalable, and can be carried out in one pot, directly dehydrogenating saturated carbonyls.

Bilateral Inguinal Hernias Masking Cryptorchidism: A Case Report.

This case report discusses the uncommon occurrence of bilateral inguinal hernias masking cryptorchidism in a 47-year-old male, emphasizing the complexities and nuances of diagnosing and managing undescended testes in adults. Cryptorchidism is most often identified and treated during infancy; however, its rare adult manifestation presents significant diagnostic challenges and is fraught with serious implications for fertility and malignancy if left untreated. The subject presented with long-standing bilateral groin discomfort and was initially evaluated using clinical examination and CT imaging, which diagnosed bilateral inguinal hernias but did not initially detect cryptorchidism.

Streamlining the Synthesis of Pyridones through Oxidative Amination of Cyclopentenones.

Herein we report the development of an oxidative amination process for the streamlined synthesis of pyridones from cyclopentenones. Cyclopentenone building blocks can undergo in situ silyl enol ether formation, followed by the introduction of a nitrogen atom into the carbon skeleton with successive aromatisation to yield pyridones. The reaction sequence is operationally simple, rapid, and carried out in one pot.

Direct Access to Quinazolines and Pyrimidines from Unprotected Indoles and Pyrroles through Nitrogen Atom Insertion.

Recent advances in single-atom insertion reactions have opened up new synthetic approaches for molecular diversification. Developing innovative strategies to directly transform biologically relevant molecules, without any prefunctionalization, is key to further expanding the scope and utility of such transformations. Herein, the direct access to quinazolines and pyrimidines from the corresponding unprotected 1-indoles and 1-pyrroles is reported, relying on the implementation of lithium bis(trimethylsilyl)amide (LiHMDS) as a novel nitrogen atom source in combination with commercially available hypervalent iodine reagents.

Nickel(I)-Phenolate Complexes: The Key to Well-Defined Ni(I) Species.

Phosphine-stabilized monovalent nickel complexes play an important role in catalysis, either as catalytically active species or as decomposition products. Most routes to access these complexes are highly ligand specific or rely on strong reducing agents. Our group recently disclosed a path to access nickel(I)-phenolate complexes from bis(1,5-cyclooctadiene)nickel(0) (Ni(cod)).

Mechanistic Investigation of the Nickel-Catalyzed Transfer Hydrocyanation of Alkynes.

The implementation of HCN-free transfer hydrocyanation reactions on laboratory scales has recently been achieved by using HCN donor reagents under nickel- and Lewis acid co-catalysis. More recently, malononitrile-based HCN donor reagents were shown to undergo the C(sp)-CN bond activation by the nickel catalyst in the absence of Lewis acids. However, there is a lack of detailed mechanistic understanding of the challenging C(sp)-CN bond cleavage step.

Skeletal metalation of lactams through a carbonyl-to-nickel-exchange logic.

Classical metalation reactions such as the metal-halogen exchange have had a transformative impact on organic synthesis owing to their broad applicability in building carbon-carbon bonds from carbon-halogen bonds. Extending the metal-halogen exchange logic to a metal-carbon exchange would enable the direct modification of carbon frameworks with new implications in retrosynthetic analysis. However, such a transformation requires the selective cleavage of highly inert chemical bonds and formation of stable intermediates amenable to further synthetic elaborations, hence its development has remained considerably challenging.

Nitrogen atom insertion into indenes to access isoquinolines.

We report a convenient protocol for a nitrogen atom insertion into indenes to afford isoquinolines. The reaction uses a combination of commercially available phenyliodine(iii) diacetate (PIDA) and ammonium carbamate as the nitrogen source to furnish a wide range of isoquinolines. Various substitution patterns and commonly used functional groups are well tolerated.

Late-stage diversification of indole skeletons through nitrogen atom insertion.

Compared with peripheral late-stage transformations mainly focusing on carbon-hydrogen functionalizations, reliable strategies to directly edit the core skeleton of pharmaceutical lead compounds still remain scarce despite the recent flurry of activity in this area. Herein, we report the skeletal editing of indoles through nitrogen atom insertion, accessing the corresponding quinazoline or quinoxaline bioisosteres by trapping of an electrophilic nitrene species generated from ammonium carbamate and hypervalent iodine. This reactivity relies on the strategic use of a silyl group as a labile protecting group that can facilitate subsequent product release.

Mechanistic Investigation of the Nickel-Catalyzed Metathesis between Aryl Thioethers and Aryl Nitriles.

Functional group metathesis is an emerging field in organic chemistry with promising synthetic applications. However, no complete mechanistic studies of these reactions have been reported to date, particularly regarding the nature of the key functional group transfer mechanism. Unraveling the mechanism of these transformations would not only allow for their further improvement but would also lead to the design of novel reactions.

Activity-Based Approach for Selective Molecular CO Sensing.

Carbon dioxide (CO) impacts every aspect of life, and numerous sensing technologies have been established to detect and monitor this ubiquitous molecule. However, its selective sensing at the molecular level remains an unmet challenge, despite the tremendous potential of such an approach for understanding this molecule's role in complex environments. In this work, we introduce a unique class of selective fluorescent carbon dioxide molecular sensors (CarboSen) that addresses these existing challenges through an activity-based approach.

One to Find Them All: A General Route to Ni(I)-Phenolate Species.

The past 20 years have seen an extensive implementation of nickel in homogeneous catalysis through the development of unique reactivity not easily achievable by using noble transition metals. Many catalytic cycles propose Ni(I) complexes as potential reactive intermediates, yet the scarcity of nickel(I) precursors and the lack of a general, non-ligand-specific protocol for their synthesis have hampered progress in this field of research. This has in turn also limited the access to novel, well-defined Ni(I) species for the development of new catalytic reactions.

A Retrospective Analysis of the Trends in Acute Appendicitis During the COVID-19 Pandemic.

The corona virus disease of 2019 (COVID-19) imposed new public health constraints that deterred people from coming to the hospital. The outcome of patients who developed appendicitis during mandated COVID-19 quarantine has yet to be examined. The main objective was to establish whether there was an increased rate of perforated appendicitis seen during COVID-19 quarantine.

An Additivity Scheme for Aromaticity: The Heteroatom Case.

The nucleus-independent chemical shift (NICS)-XY-Scan is a simple and easy tool for the quantitative measurement of the aromaticity of polycyclic aromatic hydrocarbons and identification of the existence of local and global ring currents. We recently introduced an additivity scheme that uses the NICS-XY-Scans of smaller building blocks to predict the aromatic profiles of larger polycyclic aromatic hydrocarbon systems. We now report on an expansion of the methodology to include systems of varying aromatic natures containing the heteroatoms B, N, O, and S.

Pancreatic Neuroendocrine Tumors (panNETs): Analysis of Overall Survival of Nonsurgical Management Versus Surgical Resection.

Background: Outcomes of patients with pancreatic neuroendocrine tumors (panNETs) undergoing surgical or nonsurgical management and outcomes of enucleation versus standard resection were compared.

Methods: MEDLINE, EMBASE, PubMed, Scopus, and Cochrane were queried (2000 to present). All studies comparing patients undergoing surgical versus nonsurgical treatments, or enucleation versus standard resection, were included.

Tetanus: A Potential Public Health Threat in Times of Disaster.

Background: Tetanus is a potentially fatal condition that is rare in urban environments but is seen in developing countries and post-natural-disaster. Therefore, the purpose of this report was to review the epidemiology, pathogenesis, and management of tetanus in the trauma patient.

Methods: A thorough literature review was conducted to look for the most current and thorough guidelines on the prophylaxis and treatment of tetanus.

Genetically Modified Foods: A Brief Overview of the Risk Assessment Process.

Billions of people worldwide are unable to meet their daily micro nutritional needs. Genetically modified (GM) foods, while initially developed to tolerate herbicides and resist disease and insects, have the potential to help alleviate this issue that is currently posing a serious public health concern. However, there is a negative public perception surrounding GM foods, calling for more research regarding the risks that GM foods could pose to the public, specifically on the topics of allergenicity and gene transfer.

Visible foliar injury caused by ozone alters the relationship between SPAD meter readings and chlorophyll concentrations in cutleaf coneflower.

The ability of the SPAD-502 chlorophyll meter to quantify chlorophyll amounts in ozone-affected leaves of cutleaf coneflower (Rudbeckia laciniata var. digitata) was assessed in this study. When relatively uninjured leaves were measured (percent leaf area affected by stipple less than 6%), SPAD meter readings were linearly related to total chlorophyll with an adjusted R (2) of 0.

Sub-canopy deposition of ozone in a stand of cutleaf coneflower.

Although there has been a great deal of research on ozone, interest in exposure of native, herbaceous species is relatively recent and it is still not clear what role the pollutant has in their ecological fitness. The ozone exposure of a plant is usually expressed in terms of the concentration above the canopy or as a time-weighted index. However, to understand the physiological effects of ozone it is necessary to quantify the ozone flux to individual leaves as they develop, which requires knowing the deposition velocity and concentration of the pollutant as a function of height throughout the plant canopy.

Interpreting spatial variation in ozone symptoms shown by cutleaf cone flower, Rudbeckia laciniata L.

Visible injury caused by ozone is recorded every year in native plant species growing in Great Smoky Mountains National Park (USA). One of the most sensitive species, cutleaf coneflower (Rudbeckia laciniata L.), shows great variation in symptoms between and within populations but the causes of this variation and its ecological significance are currently unknown.

Myopodin, a synaptopodin homologue, is frequently deleted in invasive prostate cancers.

Prostate cancer is one of the leading causes of cancer-related deaths for men in the United States. Like other malignancies, prostate cancer is underscored by a variety of aberrant genetic alterations during its development. Although loss of heterozygosity or allelic loss is frequently identified among prostate cancers, few genes have been identified thus far as critical to the development of invasive prostate cancers.

Mechanical devices versus antimicrobial rinses in plaque and gingivitis reduction.

The effectiveness of mechanical oral cleaning and oral antimicrobial rinses was compared for gingivitis and bacterial plaque control in 158 subjects. Teeth were brushed ad lib throughout; four of the five groups used either an interdental cleaner, dental floss, an essential oil mouthwash or a cetypyridinium mouthwash. Gingival bleeding (EIBI), visual inflammation (VGI), and tooth plaque coverage were evaluated at zero, six and 12 weeks of product use.