A designed and potentially decadentate ligand for use in lanthanide(III) catalysed biomass transformations: targeting diastereoselective trans-4,5-diaminocyclopentenone derivatives

The goal of this study was to design a ligand system which can accommodate single lanthanide(III)-ions and investigate the properties of the resulting complexes. The complexes of all the accesible lanthanides and yttrium with the new ligand LH6 = N,N′-dimethyl-N,N′-ethylene-bis(5-bromo-3-(1H-benzimidazol-2-yl)hydrazineylidene)-2-hydroxybenzylamine) were obtained in high yield at room temperature under aerobic reaction conditions. The corresponding compounds were characterised using X-ray diffraction, FT-IR, elemental analysis and the optical properties of all complexes were investigated using UV-vis and fluorescence spectroscopy. The air stable complexes efficiently transform biomass furfural to trans-4,5-cyclopentenones in high yield

A multifunctional use of bis(methylene)bis(5-bromo-2-hydroxyl salicyloylhydrazone): From metal sensing to ambient catalysis of A3 coupling reactions

The potential use of bis(methylene)bis(5-bromo-2-hydroxylsalicyloylhydrazone) as a multifunctional fluorescence sensor for Cu(2+), Ni(2+), Co(2+) and Fe(2+) ions was investigated. The optical behaviour shows an increase in an absorption band at 408 nm which can be ascribed to the d–d transition (UV-vis) of the metal ions and a concomitant decrease in fluorescence intensity at 507 nm. The crystallographic analysis shows the binding site of the sensor to two Cu(2+) ions and confirms the stoichiometry of 1 : 2 (ligand to metal) which is in good agreement with a Job plot analysis. Furthermore the Cu(2+)-complex catalyses A3 coupling reactions at 1 mol% catalytic loading; chiral propargylamine derivatives were obtained in high yield after 24 h reaction time under ambient conditions

Tetranuclear Cu(II)-chiral complexes: synthesis, characterization and biological activity

Tetranuclear chiral Cu(ii)-Schiff-base complexes S-1 and R-1, were synthesised using enantiomerically pure (S)-(H(2)vanPheol) and (R)-(H(2)vanPheol) ligands respectively in the ratio of 1 : 1 of Cu(NO(3))(2) to (S/R)-(H(2)vanPheol) in MeOH at room temperature. A pair of polynuclear chiral Cu(ii)-cluster complexes were characterized using single-crystal X-ray diffraction, elemental analysis, infrared and CD spectroscopy. The results revealed the importance of these chiral ligands encouraging the arrangement of copper metal in non-centrosymmetric polar packing. The potential of the novel [Cu(4)(S/R-vanPheol)(2)(S/R-HvanPheol)(2)(CH(3)OH)(2)](NO(3))(2) complexes as biologically active compounds was assessed in particular regarding their anti-proliferative and anti-microbial properties

Polarity sensitive bioorthogonally applicable far-red emitting labels for postsynthetic nucleic acid labeling by copper-catalyzed and copper-free cycloaddition

Two series of new, water-soluble, membrane-permeable, far-red/NIR emitting benzothiazolium-based fluorescent labels with large Stokes’ shifts were synthesized that can be conjugated to alkyne-modified biomolecules through their azide moiety via azide–alkyne cycloaddition. We have used these azide bearing labels to make fluorescent DNA constructs using copper-catalyzed “click” reaction. All dyes showed good or remarkable fluorescence intensity enhancement upon conjugation to DNA. We also investigated the possibility to incorporate the benzocyclooctyne motif through rigid (ethnynyl) or flexible (ethyl) linkers into the DNA, thus enabling copper-free labeling schemes. We observed that there is a marked difference between the two linkers applied in terms of optical properties of the labeled oligonucleotides. We have also tested the in vivo labeling potential of these newly synthesized dyes on HeLa cells previously transfected with cyclooctynylated DNA. Confocal fluorescent images showed that the dyes are all able to cross the membrane and suitable for background-fluorescence free fluorescent tagging of nucleic acids. Moreover, we have observed different accumulation of the two dye series in the endosomal particles, or in the nuclei, respectively

Synthesis of <i>gem</i>-Difluoromethylenated Bicyclo[<i>m.n.</i>0]alkan-1-ols and Their Ring-Expansion to <i>gem</i>-Difluoromethylenated Macrocyclic Lactones

Fluoride-catalyzed stereoselective nucleophilic addition of PhSCF₂SiMe₃ (<b>1</b>) to α-carboethoxycycloalkanones <b>2</b> followed by intramolecular radical cyclization of the resulting <i>cis</i>-<b>3</b> adduct afforded the corresponding <i>gem</i>-difluoromethylenated bicyclic compounds <b>4</b>, which underwent ring-expansion followed by the Baeyer–Villiger-type oxidation of the resulting macrocyclic ketone intermediates to give <i>gem</i>-difluoromethylenated macrocyclic lactones <b>5</b>