Synthesis of a Bicyclic Diamine Derived from Kemp's Acid

A bicyclic diamine with defined and stable conformation in solution was prepared from Kemp's triacid. The efficient four-step synthesis of the Boc-protected diamine requires only a single purification by column chromatography. X-ray analysis and NMR spectroscopy confirm the structure of the diamine in the solid state and in solution.     

Silica Sulfuric Acid: An Efficient,Reusable, Heterogeneous Catalyst for the One-Pot,Five-Component Synthesis of Highly Functionalized Piperidine Derivatives

A series of highly functionalized piperidine derivatives was synthesized through one-pot, five-component reaction of aldehydes, amines, and β-ketoesters. Silica sulfuric acid efficiently catalyzes the reaction to afford the corresponding piperidine derivatives in good yields. As a representative example, heating of 4-methylaninle, 4-fluorobezaldehyde, and methyl-acetoacetate in methanol in the presence of silica sulfuric acid furnished the corresponding ethyl 2,6-bis(4-fluorophenyl)-1-p-tolyl-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate in excellent yield (85%). Most of the synthesized compounds were screened in vitro for their antibacterial and antifungal activities. Most of compounds showed significant antibacterial activity.     

New Cytotoxic Triterpenoids from the Aerial Parts of Euphorbia sieboldiana

Phytochemical investigation of the EtOH extract of Euphorbia sieboldiana led to the isolation of four new oleanane‐type triterpenoids, (1β,2α,3β,19β)‐1,2,3,19‐tetrahydroxyolean‐12‐en‐28‐oic acid, (1β,3β,19β)‐1,3,19‐trihydroxyolean‐12‐en‐28‐oic acid, (1β,2α,3β,16β,19β)‐1,2,3,16,19‐pentahydroxyolean‐12‐en‐28‐oic acid, and (1β,2α,3β,19β,23)‐1,2,3,19,23‐pentahydroxyolean‐12‐en‐28‐oic acid, along with 16 known compounds. Their structures were established by extensive 1D‐ and 2D‐NMR, as well as other spectral analyses. Biological evaluation of the four new triterpenoids revealed potent cytotoxic activities against HeLa and Hep‐G2 cells.     

Choline Chloride/Urea Ionic Liquid Catalyzed a Convenient One-Pot Synthesis of Indole-3-propanamide Derivatives

A sequential three-component reaction of aromatic aldehydes with Meldrum's acid and N-methyl indole in the presence of choline chloride/urea ionic liquid as green catalyst has been described. In this one-pot multicomponent reaction, a series of indole-3-propanamide derivatives were synthesized with good to excellent yields. This methodology shows several advantages including fast reaction, easy isolation, operational simplicity that make it a useful and attractive option for the library generation of indole-3-propanamides (5a–l) for drug discovery.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resources: Full experimental and spectral details.]     

Mesomorphous Structure and Electrochemical Behavior of Polyelectrolyte-Ferrocenyl Surfactant Complexes

Redox-active polyelectrolyte-surfactant complexes (PSC) were prepared via the ionic self-assembly of sodium polyacrylate (PAAS) and ferrocenyl surfactant, n-alkyl (ferrocenylmethyl)ammonium bromide (Fcn, n = 8, 12, 16, where n is the carbon number of the alkyl chain), in solution. The obtained PAAS-Fcn complex exhibited crystalline and lamellar mesomorphous structure. Moreover, the ferrocenyl moieties formed H-aggregation in the solid complex as known from the blue shift in the ultraviolet-visible spectrum. Cyclic voltammogram (CV) measurements indicated that the reversibility of the electrode process became worse when the surfactant tail length increases because of the more ordered packing in the complex film formed by longer surfactant tails. The present results demonstrate that the electrochemical activity of the redox-active polyacrylate-ferrocenyl surfactant complex can be easily tuned by changing the surfactant tail length. Our work provides a simple and facile approach to the preparation of redox-active polymers with ordered mesomorphous structure by the ionic self-assembly.     

Crystal Structure of 2-（2-Carboxy-4-hydroxy-6- methoxyphenoxy）-3,5-dichloro-6-hydroxy- 4-methylbenzoic Acid 1-Methyl Ester

The title compound, neogeodin hydrate （C17H14C1208, CAS： 94540-50-8）, was derived from marine fungus Aspergilhts terreus CRIM301. It was unequivocally characterized by IR, NMR spectroscopies, and single-crystal X-ray crystallography and tested for various biological activities. Neogeodin hydrate crystallizes in the triclinic space group P1 with a = 8.1159（5） A, b = 8.2472（4） A, c= 14.1278（7） A, a = 81.448（2）°, β = 84.860（2）°, γ= 70.400（2）°, V = 880.13（8） A3; Z = 2. It comprises a diphenyl ether, asterric acid skeleton and dichloro substituents. The methoxyphenoxy rings of the inversely related molecules form a ribbon-like structure that is stabilized by O-H...O hydrogen bonds through the doubly disordered carboxyl groups and by C-H...O interactions, generating the same R22（8） ring motif. The chlorinated methylbenzoate rings, making mostly a right angle, link the parallel upper and lower ribbons via bifurcated O-H...O and C-H...O hydrogen bonds, yielding endless channels. The channels formed are further sustained by C-H...O and π...π interactions Neogeodin hydrate exhibits inhibition against superoxide anion radical formation in the xanthine/xanthine oxidase （XXO） assay, but has no aromatase inhibitory activity.     

Nourdin–Peccati analysis on Wiener and Wiener–Poisson space for general distributions

Given a reference random variable, we study the solution of its Stein equation and obtain universal bounds on its first and second derivatives. We then extend the analysis of Nourdin and Peccati by bounding the Fortet–Mourier and Wasserstein distances from more general random variables such as members of the Exponential and Pearson families. Using these results, we obtain non-central limit theorems, generalizing the ideas applied to their analysis of convergence to Normal random variables. We do these in both Wiener space and the more general Wiener–Poisson space. In the former space, we study conditions for convergence under several particular cases and characterize when two random variables have the same distribution. In the latter space we give sufficient conditions for a sequence of multiple (Wiener–Poisson) integrals to converge to a Normal random variable.     

Total synthesis of fuzinoside

The first total syntheses of fuzinoside (1b) were achieved from d-galactose through two strategies (BCA and ABC) in 11 (total yield: 5.0%) and 15 (total yield: 3.7%) steps, respectively. Comparison of NMR data of synthetic compound 1b and those of the fuzinoside isolated from the lateral roots of Aconitum carmicaelii suggests that the structure reported in the literature ^1 and 2 might not be accurate. The synthetic fuzinoside (1b) exhibited moderate cardiac activity in the isolated bullfrog heart assay.     

Simple and practical method for selective acylation of primary hydroxy group catalyzed by N-methyl-2-phenylimidazole (Ph-NMI) or 2-phenylimidazo[2,1-b]benzothiazoles (Ph-IBT)

N-Methyl-2-phenylimidazole (Ph-NMI) and 2-phenylimidazo[2,1-b]benzothiazoles (Ph-IBT) catalyzed selective acylation of primary alcohols using acid anhydrides. The Ph-NMI- or Ph-IBT-catalyzed reaction using (PhCO)₂O as an acylating agent could particularly acylate the primary hydroxy group of 1,n-diols (n ⩾ 3) with a high, synthetically useful selectivity.     

The Process of Acetonitrile Synthesis over γ-Al2O3 Promoted by Phosphoric Acid Catalysts

The influence of principal parameters (reaction temperature, ratio of acetic acid and ammonia, composition of reactionary mixture and promotion of catalysts) on the selectivity and yield of the desired product was studied in the reaction of catalytic acetonitrile synthesis by ammonolysis of acetic acid. The processing of γ-Al₂O₃ by phosphoric acid increases amount of the centers, on which carries out reaction of acetamide dehydration. The kinetic model of a limiting stage of reaction – the acetamide dehydration to acetonitrile was suggested. In the process of ammonolysis of acetic acid it was demonstrated that the use of catalysts promoted by phosphoric acid and ratio NH₃:CH₃COOH=(3-4):1 at temperatures of a reactor 360-390°С leads to the increase of acetonitrile productivity to 0.7-0.8 g/cm³·h and allows to minimize formation of by-products.