Conceptualization and Synthesis of the First Inosito-Inositol (Decahydroxydecalin,DHD): In silico Binding to β-Amyloid Protein

Previously unknown entities in the form of 1,2,3,4,5,6,7,8,9,10-decahydroxydecalins (DHDs) have been conceptualized and the first member of this class, an inosito-inositol, has been synthesized from aromatic hydrocarbon naphthalene following a flexible strategy that is amenable to diversity creation. The DHD accessed here has been subjected to preliminary in silico evaluation with Aβ and may hold some promise in Alzheimer's disease therapeutics.     

Boron doping and structure control of carbon materials for supercapacitor application: the effect of freeze-drying and air-drying for porosity engineering

Journal of Solid State Electrochemistry - In the present work, we demonstrate a strategy of combining boron doping and porosity engineering for a highly modulated carbon component and pore...     

Boundary Crossing Probabilities of Jump Diffusion Processes to Time-Dependent Boundaries

Methodology and Computing in Applied Probability - The finite Markov chain imbedding technique has been used to compute the boundary crossing probabilities of one and higher-dimensional Brownian...     

Leibniz Conformal Algebras of Rank Two

We classify all Leibniz conformal algebras of rank two.     

1,10-Phenanthroline: A versatile ligand to promote copper-catalyzed cascade reactions

Ligand-promoted copper-catalyzed cascade reactions have become a robust tool for the synthesis of cyclic compounds. Although numerous ligands have been developed, this review focuses on the introduction of commercially available 1,10-phenanthroline-promoted copper-catalyzed cascade reactions in recent years. Moreover, based on original articles, this review highlights product yields in the presence and absence of the ligand, and the possible mechanistic role of the ‘copper/1,10-phenanthroline’ catalytic system.     

Exciton Interactions,Excimer Formation,and [2π+2π] Photodimerization in Nonconjugated Curcuminoid-BF2 Dimers

We describe the synthesis of a series of covalently linked dimers of quadrupolar curcuminoid-BF₂ dyes and the detailed investigation of their solvent-dependent spectroscopic and photophysical properties. In solvents of low polarity, intramolecular folding induces the formation of aggregated chromophores, the UV/Vis absorption spectra of which display the optical signature characteristic of weakly-coupled H-aggregates. The extent of folding and, in turn, of ground-state aggregation is strongly dependent on the nature of the flexible linker. Steady-state and time-resolved fluorescence emission spectroscopies show that the Frenkel exciton relaxes into a fluorescent symmetrical excimer state with a long lifetime. Furthermore, our in-depth studies show that a weakly emitting excimer lies on the pathway toward a photocyclomer. Two-dimensional ¹H NMR spectroscopy and density functional theory (DFT) allowed the structure of the photoproduct to be established. To our knowledge, this represents the first example of a [2π+2π] photodimerization of the curcuminoid chromophore.     

Transition-Metal-Free Multiple Functionalization of Piperidines to 4-Substituted and 3,4-Disubstituted 2-Piperidinones

Remote and multiple functionalization of piperidines without the use of transition-metal catalysts and elaborate directing groups is one of the major challenges in organic synthesis. Herein is reported an unprecedented two-step protocol that enables the multiple functionalization of piperidines to either 4-substituted or trans-3,4-disubstituted 2-piperidones. First, by exploiting the duality of TEMPO reactivity, which under oxidative and thermal conditions fluctuates between cationic and persistent-radical form, a novel multiple C(sp³)-H oxidation of piperidines to α,β-unsaturated 2-piperidones was developed. Second, the intrinsic low reactivity of the unsaturated piperidones toward conjugated Grignard additions was overcome by using trimethylsilyl chloride (TMSCl) as Lewis acid. Subsequently, conjugated Grignard addition/electrophilic trapping protocol provided substituted 2-piperidone intermediates, some of which were then transformed into pharmaceutical alkaloids.     

Hantzsch Ester as a Visible-Light Photoredox Catalyst for Transition-Metal-Free Coupling of Arylhalides and Arylsulfinates

Diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate (HEH) has been utilized as a visible-light photoredox catalyst for the cross coupling of arylhalides and arylsulfinates without transition metal, sacrificial agent, and mediator. This method is compatible with various functional groups and provides diaryl sulfones in good to high yields. Mechanistic studies indicate that this reaction undergoes the stepwise light irradiation of HE⁻, single electron transfer (SET) in donor–acceptor complex (DAC) from *HE⁻ to arylhalide, trapping of aryl radical with sulfinate, and SET oxidation of sulfone radical anion by HE^. to sulfone by the DAC method.     

Divergent 2-Chloroquinazolin-4(3H)-one Rearrangement: Twisted-Cyclic Guanidine Formation or Ring-Fused N-Acylguanidines via a Domino Process

A highly efficient 2-chloroquinazolin-4(3H)-one rearrangement was developed that predictably generates either twisted-cyclic or ring-fused guanidines in a single operation, depending on the presence of a primary versus secondary amine in the accompanying diamine reagent. Exclusive formation of twisted-cyclic guanidines results from pairing 2-chloroquinazolinones with secondary diamines. Use of primary amine-containing diamines permits a domino quinazolinone rearrangement/intramolecular cyclization, gated through (E)-twisted-cyclic guanidines, to afford ring-fused N-acylguanidines. This scalable, structurally tolerant transformation generated 55 guanidines and delivered twisted-cyclic guanidines with robust plasma stability and an abbreviated total synthesis of an antitumor ring-fused guanidine (4 steps, 55 % yield).     

Crystalline Nitridophosphates by Ammonothermal Synthesis

Nitridophosphates are a well-studied class of compounds with high structural diversity. However, their synthesis is quite challenging, particularly due to the limited thermal stability of starting materials like P₃N₅. Typically, it requires even high-pressure techniques (e.g. multianvil) in most cases. Herein, we establish the ammonothermal method as a versatile synthetic tool to access nitridophosphates with different degrees of condensation. α-Li₁₀P₄N₁₀, β-Li₁₀P₄N₁₀, Li₁₈P₆N₁₆, Ca₂PN₃, SrP₈N₁₄, and LiPN₂ were synthesized in supercritical NH₃ at temperatures and pressures up to 1070 K and 200 MPa employing ammonobasic conditions. The products were analyzed by powder X-ray diffraction, energy dispersive X-ray spectroscopy, and FTIR spectroscopy. Moreover, we established red phosphorus as a starting material for nitridophosphate synthesis instead of commonly used and not readily available precursors, such as P₃N₅. This opens a promising preparative access to the emerging compound class of nitridophosphates.