Abstract An atom-economic and diazo-free strategy for the construction of novel pseudo anomeric C-1 alkenyl spirocyclopropyl sugars is described. Leveraging the 1,2-migration pathway of propargyl esters under gold(I) catalysis, easily available exo-glycals undergo β-selective alkenylcarbenoid…
Abstract Analogous to O-glycosides, C-glycosides are natural products exhibiting various bioactivities. Alkynyl C-glycosides represent important key intermediates toward more complex derivatives; however, a convenient access through a single catalytic and highly stereocontrolled step remains an…
Abstract Herein, we report the first visible-light-induced strategy for the rapid synthesis of densely functionalized α- and γ-phosphorylated β-sulfonyl enamines in a regio- and stereoselective fashion from N-sulfonyl allenamides and H-phosphine oxides. The transformation displays a broad…
Abstract This work details the synthesis and characterization of low-coordinate Zn(II)-based organocations [(NHC)Zn(R)]+ incorporating extremely bulky NHCs [ITr] and [IAd] ([ITr] = ([ITr] = [(HCNCPh3)2C:]; [IAd] = [(HCNAd)2C:], Ad = adamantyl)). Their structural features and particularities are…
Abstract he present report describes the first use of unprotected and “free” N-heterocyclic carbenes (NHCs), such as IMes, IPr and air-stable Cl-IPr carbenes, as single component initiators for the alternating ring-opening co-polymerization (ROCOP) of cyclic anhydrides (phthalic anhydride, PA;…
Abstract In recent works by Yalouz et al. (J. Chem. Phys. 157, 214112, 2022) and Sekaran et al. (Phys. Rev. B 104, 035121, 2021; Computation 10, 45, 2022), Density Matrix Embedding Theory (DMET) has been reformulated through the use of the Householder transformation as a novel tool to embed a…
Abstract A seed recovered during archaeological excavations of a cave in the Judean desert was germinated, with radiocarbon analysis indicating an age of 993 CE– 1202 calCE. DNA sequencing and phylogenetic analysis identified the seedling as belonging to the angiosperm genus Commiphora Jacq.,…
Abstract Strigolactones exhibit dual functionality as regulators of plant architecture and signaling molecules in the rhizosphere. The important model crop rice exudes a blend of different strigolactones from its roots. Here, we identify the inaugural noncanonical strigolactone, 4-oxo-methyl…
Abstract Photoallergic contact dermatitis is a skin disease caused by combined exposure to photoreactive chemicals and sunlight. Exposure to allergens and the risk of skin sensitization is an essential regulatory issue within the industry. Yet, only few non-validated assays for photoallergy…
Abstract Organofluorines have a broad range of industrial applications, such as pharmaceutics, liquid crystal displays (LCD), solar cells, textiles, and construction coatings, and are used in peptidomimetics, surfactants, refrigerants, anesthetics, and agrochemicals. Among them are versatile…
Abstract A method for the construction of trifluorinated-5-methylenepyrrolidinone is reported. This strategy combines an acid-catalyzed two-carbon homologation process between ynamides and aldehydes, providing CF3-substituted dienes followed by a metal-free domino…
Graphical Abstract An asymmetric diradical was synthesized by grafting a nitroxide radical onto the [Y(Pc)2]⋅ radical system. The molecule was shown to exhibit a weak exchange interaction between its two radical units. The g-asymmetry combined with the magnetic interaction led to the electron…
Abstract The controlled growth of self-assembled networks on surfaces based on viologen salts is a major scientific challenge due to their unique electronic properties. The combination of solid-state NMR spectroscopy and atomic force microscopy at ambient conditions can unravel the fine…
Abstract This work merges two different types of many-electron ensembles, namely, the Theophilou-Gross-Oliveira-Kohn ensembles of ground and neutrally excited states, and the more recent ð‘-centered ensembles of neutral and charged ground states. On that basis, an in-principle exact and general,…
Summary Rigid terdentate ‘pincer' ligands containing a bridgehead N-heterocyclic carbene (NHC) donor attract considerable interest as spectators in transition metal complexes with broad scope and potential applications in the fields of catalysis, medicinal chemistry and material science. This…
Summary Pyridine Ring-Expanded dicarbene Pincer ligands were synthesized and some representative complexes with Ni and Cr show distinct geometrical and electronic characteristics from analogues with 5-membered ring heterocycles, opening new possibilities for pincer ligands featuring carbene…
Résumé Une formulation alternative de la théorie de la fonctionnelle de la densité (DFT) au-delà de l'approximation usuelle de Born—Oppenheimer (qui n'est plus valide, par exemple, lorsque l'on simule des processus photochimiques) est proposée dans ce travail. Dans cette approche, les densités…
Résumé Une description en principe exacte des excitations électroniques “double” (promotion de deux électrons des orbitales occupées dans l'état fondamental vers des orbitales de plus hautes énergies) en théorie de la fonctionnelle de la densité (DFT) est proposée. Ces dernières sont absentes des…
Abstract CPPs, or Cell-Penetrating Peptides, offer invaluable utility in disease treatment due to their ability to transport various therapeutic molecules across cellular membranes. Their unique characteristics, such as biocompatibility and low immunogenicity, make them ideal candidates for…
Abstract Metal ion-catalysed overproduction of reactive oxygen species (ROS) are believed to contribute significantly to oxidative stress and be involved in several biological processes, from immune defence to development of diseases. Among the essential metal ions, copper is one of the most…
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