One-pot synthesis of a new generation of hybrid bisphosphonate polyoxometalate gold nanoparticles as antibiofilm agents.

A reduced polyoxovanadate functionalized with bisphosphonate molecules was synthesized and used to prepare in one step hybrid organic-inorganic polyoxometalate decorated gold nanoparticles. These new composites were shown to strongly inhibit P. aeruginosa and S. epidermidis biofilm growth, with the three components constituting the nanoparticles (Au0 core, vanadium and alendronate) acting synergistically.

Correction: One-pot synthesis of a new generation of hybrid bisphosphonate polyoxometalate gold nanoparticles as antibiofilm agents.

[This corrects the article DOI: 10.1039/C9NA00401G.].

Synthesis of homopropargylamines from 2-cyanoazetidines.

2-Cyanoazetidines, easily accessible from ß-amino alcohols, undergo ring-cleavage upon reaction with trimethylsilylazide and catalytic amounts of Bu2SnO, to give the corresponding homopropargylamines which are isolated as their N-Boc protected derivatives. The scope of this reaction, which constitutes a new way to access these highly relevant building blocks, is examined in detail. The proposed mechanism involves a tin-catalyzed cycloaddition of the nitrile moiety with the azide to give the corresponding tetrazole, which decomposes with the extrusion of two molecules of dinitrogen to produce an intermediate vinylidene carbene that finally evolves to give the alkyne.

Construction of enantioenriched polysubstituted hexahydropyridazines via a sequential multicatalytic process merging palladium catalysis and aminocatalysis.

An efficient multicatalytic strategy for the construction of nitrogen-containing heterocycles has been reported. The powerful combination of organic and metal catalysis in a single vessel allowed the formation of enantioenriched polysubstituted cyclic 6-membered hydrazines bearing a quaternary stereocenter in good yields and selectivities.

3D shapes of aryl(dihydro)naphthothiophenes: a comprehensive and structural study.

Convenient access to new aryl(dihydro)naphthothiophenes is described using a common ß-chloroacrolein derivative. Our strategy is based on the construction of a condensed thiophene ring prior to a Suzuki-Miyaura coupling and allowed installing various substituents at the molecular platform. The overall shapes of these architectures were confirmed by X-ray analyses and were in good agreement with theoretical calculations. It has been established that the relative orientation between all fragments that composed molecules within this series is strongly related to both steric and electronic factors. Contribution of these key parameters revealed to be crucial to rationalize attempts to prepare fluorenone and fluorene derivatives from aryl(dihydro)naphthothiophene platforms.

Aza-[2,3]-Wittig Sigmatropic Rearrangement of Allylic Tertiary Amines: A Successful Example with High Chirality Transfer.

We report herein a successful example of an aza-[2,3]-Wittig rearrangement in an allylic tertiary N,N-dibenzyl amine derived from (S)-alaninol or (S)-isoleucinol. This reaction occurs upon metalation at the benzylic position with a mixture of butyllithium/diisopropylamine/potassium t-butoxide and proceeds with a high 1,3 transfer of chirality.

N- and C-alkylation of seven-membered iminosugars generates potent glucocerebrosidase inhibitors and F508del-CFTR correctors.

The glycosidase inhibitory properties of synthetic C-alkyl and N-alkyl six-membered iminosugars have been extensively studied leading to therapeutic candidates. The related seven-membered iminocyclitols have been less examined despite the report of promising structures. Using an in house ring enlargement/C-alkylation as well as cross-metathesis methodologies as the key steps, we have undertaken the synthesis and biological evaluation of a library of fourteen 2C- and eight N-alkyl tetrahydroxylated azepanes starting from an easily available glucopyranose-derived azidolactol. Four, six, nine and twelve carbon atom alkyl chains have been introduced. The study of two distinct D-gluco and L-ido stereochemistries for the tetrol pattern as well as R and S configurations for the C-2 carbon bearing the C-alkyl chain is reported. We observed that C-alkylation of the L-ido tetrahydroxylated azepane converts it from an α-L-fucosidase to a ß-glucosidase and ß-galactosidase inhibitor while N-alkylation of the D-gluco iminosugar significantly improves its inhibition profile leading to potent ß-glucosidase, ß-galactosidase, α-L-rhamnosidase and ß-glucuronidase inhibitors whatever the stereochemistry of the alkyl chain. Interestingly, the N-alkyl chain length usually parallels the azepane inhibitor potency as exemplified by the identification of a potent glucocerebrosidase inhibitor (Ki 1 µM) bearing a twelve carbon atom chain. Additionally, several C-alkyl azepanes demonstrated promising F508del-CFTR correction unlike the parent tetrahydroxyazepanes. None of the C-alkyl and N-alkyl azepanes did inhibit ER α-glucosidases I or II.

A microporous scandium terephthalate, Sc2(O2CC6H4CO2)3, with high thermal stability.

A scandium terephthalate with isolated ScO6 octahedra and fully-linked carboxylate groups is prepared hydrothermally and possesses a novel hybrid framework structure with high thermal stability and a pore volume for N2 adsorption of 0.26 cm(3) g(-1) at 77 K.

VIII(OH)[O2C-C6H4-CO2].(HO2C-C6H4-CO2H)x(DMF)y(H2O)z(or MIL-68), a new vanadocarboxylate with a large pore hybrid topology: reticular synthesis with infinite inorganic building blocks?

V(III)(OH)[O(2)C-C(6)H(4)-CO(2)].(HO(2)C-C(6)H(4)-O(2)H)(x)(DMF)(y)(H(2)O)(z) or MIL-68 was solvothermally synthesised in a non-aqueous medium. Its structure, built up from octahedral chains connected by terephthalate linkers, exhibits large hexagonal channels containing different occluded moieties. Their irreversible removal releases a specific surface area of 603(22) m(2).g(-1)(BET).

Structural characterization and magnetic properties of sandwich-type tungstoarsenate complexes. Study of a mixed-valent VIV2/VV heteropolyanion.

Complexes K11Na1[As2W18(Mn(H2O))3O66]x27H2O (1) and Na12[As2W18(Co(H2O))3O66]x34H2O (2) have been characterized. 1 crystallizes in the orthorhombic space group Pnma, with a = 30.6484(4) A, b = 14.9946(2) A, and c = 19.17080(10) A (Z = 4), while 2 crystallizes in the monoclinic space group C2/c, with a = 14.124(2) A, b = 23.294(3) A, c = 32.247(3) A, and beta = 98.935(10) degrees (Z = 4). Structures of the anions of 1 and 2 are similar, the divalent metals adopting a square pyramidal environment. K11[As2W18(VO)3O66]x23H2O (3) crystallizes in the orthorhombic space group Pnma, with a = 30.6240(5) A, b = 14.9861(2) A, and c = 19.2651(3) A (Z = 4). The structure has revealed a disorder on two of the three metals linking the [alpha-AsW9O33]9- parts. For these two vanadium atoms, the V=O bonds are directed alternatively toward the inside or the outside of the [alpha-AsW9O33]9- cavity. The remaining vanadium shows a V=O bond always directed toward the outside of the cavity. Titration of VIV by CeIV revealed that 3 is the mixed-valent VIV2VV species. Magnetic measurements are in agreement with this formulation. The high-temperature molar magnetic susceptibility of a powdered sample of 3 clearly confirms the presence of two d1 centers. The two VIV are antiferromagnetically coupled, with J = -2.9 cm-1 and g = 1.93. Crystallographic data do not permit the location of the two VIV to be distinguished from the location of the VV. As expected, the Mn(II) are very weakly antiferromagnetically coupled in compound 1. The complex Na8[Ni(H2O)6]2[As2W18(Ni(H2O))3O66]x20H2O (4) has been synthesized. The anion crystallized with two octahedral [Ni(H2O)6]2+ as counterions. Magnetic data have been fitted assuming that the only exchange-coupled centers are the nickels of the polyanion. 4 exhibits an antiferromagnetic coupling with J = -1.7 cm-1, g = 2.27, and theta = -1.5 K.

Tetraaquabis(3,5-dicarboxybenzoato-O)cobalt(II)

The hydrothermal reaction of cobalt(II) chloride with trimesate (3, 5-dicarboxybenzoate) ions in aqueous solution gives the novel title complex, [Co(C(9)H(5)O(6))(2)(H(2)O)(4)]. The Co(II) ion lies on an inversion centre and is octahedrally coordinated to two trimesate anions and four water molecules. Hydrogen bonds ensure the three-dimensional architecture of the structure.

[H3N]

The structure of the title compound, pentane-1,5-diammonium aluminium(III) hydrogen bis(phosphate), (C(5)H(16)N(2))[AlP(2)O(8)H], obtained solvothermally at 473 K, has been determined by single-crystal X-ray diffraction. It consists of one-dimensional [AlP(2)O(8)H](2-) macroanions, connected to each other by pentanediammonium cations. Contrary to similar compounds with P/Al = 2, the three-dimensional structure is mainly obtained via a network of hydrogen bonds.