Regio- and Stereochemical Aspects of the Palladium-Catalyzed Desilylation-Arylation of Substituted Vinylsilanes

The palladium-catalyzed desilylation-arylation of substituted vinylsilanes by p-iodoanisole in the presence of bidentate phosphine ligands is described. Apart from enhancing the rate of the reaction considerably, heteroatom-based functional groups in the vinylsilane moiety have a profound influence on the regiochemistry. A catalytic cycle for the chelation-controlled desilylation-arylation reaction involving five- and six-membered chelate rings is proposed.     

A borel-weil-bott approach to representations of sl q (2, ℂ)

We use a quite concrete and simple realization of sl _q (2, ) involving finite difference operators. We interpret them as derivations (in the noncommutative sense) on a suitable graded algebra, which gives rise to the noncommutative scheme ¹ II ^1* as the counterpart of the standard ¹ = Sl(2, )/B.     

Cationic cobalt(I) carbonyl complexes containing secondary or tertiary phosphines. A direct synthesis from cobalt(II) salts

Cobalt(I) carbonyl complexes of formula [Co(CO)_n(P)_5?n]ClO₄ (n = 1, 2, 3; P = secondary or tertiary phosphine) have been prepared by reaction of CO under ambient conditions with Co(ClO₄)₂ · 6H₂O and phosphine in isopropyl alcohol. The chemical and spectroscopic properties of these complexes are described and the stoichiometry and mechanism of the carbonylation reaction discussed.     

Preparative and NMR studies of 1,3-dienecobalt(I) complexes

The synthesis and the characterization of cobalt(I) complexes of the type [Co(diene)(phosphine)₃]Y (diene = 1,3-butadiene and isoprene; phosphine = PMe₃, PMe₂Ph, and HPPh₂; Y = ClO₄, BF₄, or BPh₄) are reported. The fluxional nature of the five-coordinate cations [Co(diene)(phosphine)₃]⁺ is shown by variable-temperature NMR spectroscopy (¹H and ³¹P). Low-temperature spectra are consistent with a square-pyramidal structure in which the diene occupies two basal coordination sites.     

Regiocontrolled synthesis of enantiopure 3,3'-thiosubstituted biphenyls

Sulfenylation of 6,6'-dimethoxy-2,2'-dihydroxybiphenyl, used as a racemic mixture and single enantiomers, by phthalimidesulfenyl chloride afforded the corresponding 3,3'-N,N'-dithiophthalimide with complete regioselectivity. Simple manipulations of the latter compound allowed access to the corresponding bis-thiol or o-thioquinone as useful intermediates for the synthesis of new sulfur-containing open-chain and macrocyclic C(2) enantiopure ligands. The application of this methodology to the preparation of a biphenyl bearing two cysteine units as potential HIV-1 protease inhibitor is also described.     

Rapid access to 3-(N-substituted)-aminoquinolin-2(1H)-ones using palladium-catalyzed C-N bond coupling reaction

A series of 3-(N-substituted)-aminoquinolin-2(1H)-ones have been synthesized by the palladium-catalyzed C-N coupling reaction starting from 3-bromoquinolin-2-(1H)-ones. Various nucleophiles including amines, amides, sulfonamides, carbamates and ureas have been used successfully. In all the cases, the reactions take place rapidly in 1,4-dioxane and proceed in good to excellent yield using palladium acetate as a catalyst, Xantphos as a ligand and Cs₂CO₃ as a base.     

Probing the Helical Secondary Structure of Short-Chain β-Peptides

Structural prerequisites for the stability of the 3₁ helix of β-peptides can be defined from inspection of models (Figs. 1 and 2): lateral non-H-substituents in 2- and 3-position on the 3-amino-acid residues of the helix are allowed, axial ones are forbidden. To be able to test this prediction, we synthesized a series of heptapeptide derivatives Boc-(β-HVal-β-HAla-β-HLeu-Xaa-β-HVal-β-HAla-β-HLeu)-OMe 13–22 (Xaa = α- or β-amino-acid residue) and a β-depsipeptide 25 with a central (S)-3-hydroxybutanoic-acid residue (Xaa = –OCH(Me)CH₂C(O)–) (Schemes 1 3). Detailed NMR analysis (DQF-COSY, HSQC, HMBC, ROESY, and TOCSY experiments) in methanol solution of the β-hexapeptide H(-β-HVal-β-HAla-β-HLeu)₂-OH ( 1 ) and of the β-heptapeptide H-β-HVal-β-HAla-β-HLeu-(S,S)-β-HAla(αMe)-β-HVal-β-HAla- β-HLeu-OH ( 22 ), with a central (2S,3S)-3-amino-2-methylbutanoic-acid residue, confirm the helical structure of such β-peptides (previously discovered in pyridine solution) (Fig.3 and Tables 1–5). The CD spectra of helical β-peptides, the residues of which were prepared by (retentive) Arndt-Eistert homologation of the (S)- or L -α-amino acids, show a trough at 215 nm. Thus, this characteristic pattern of the CD spectra was taken as an indicator for the presence of a helix in methanol solutions of compounds 13–22 and 25 (including partially and fully deprotected forms) (Figs.4–6). The results fully confirm predicted structural effects: incorporation of a single ‘wrong’ residue ((R)-β-HAla, β-HAib, (R,S)-β-HAla(α Me), or N-Me-β-HAla) in the central position of the β-heptapeptide derivatives A (see 17, 18, 20 , or 21 , resp.) causes the CD minimum to disappear. Also, the β-heptadepsipetide 25 (missing H-bond) and the β-heptapeptide analogs with a single α-amino-acid moiety in the middle ( 13 and 14 ) are not helical, according to this analysis. An interesting case is the heptapeptide 15 with the central achiral, unsubstituted 3-aminopropanoic-acid moiety: helical conformation appears to depend upon the presence or absence of terminal protection and upon the solvent (MeOH vs. MeOH/H₂O).     

Phenol photonitration

This paper presents some new data on nitrophenol formation from phenol under illumination, and reviews the studies performed on phenol photonitration, from its discovery in 1988 to the very recent elucidation of its reaction pathway by the authors. Recent experimental results account for the pH effect on phenol photonitration. The nitrogen sources so far investigated are nitrate and nitrite, which undergo photolysis upon absorption of near-UV light. These studies have given a relevant information on the role of both nitrate and nitrite as environmental factors. Such processes can take place both in natural waters and in atmospheric hydrometeors.     

Binding and condensation of plasmid DNA onto functionalized carbon nanotubes: toward the construction of nanotube-based gene delivery vectors

Carbon nanotubes (CNTs) constitute a class of nanomaterials that possess characteristics suitable for a variety of possible applications. Their compatibility with aqueous environments has been made possible by the chemical functionalization of their surface, allowing for exploration of their interactions with biological components including mammalian cells. Functionalized CNTs (f-CNTs) are being intensively explored in advanced biotechnological applications ranging from molecular biosensors to cellular growth substrates. We have been exploring the potential of f-CNTs as delivery vehicles of biologically active molecules in view of possible biomedical applications, including vaccination and gene delivery. Recently we reported the capability of ammonium-functionalized single-walled CNTs to penetrate human and murine cells and facilitate the delivery of plasmid DNA leading to expression of marker genes. To optimize f-CNTs as gene delivery vehicles, it is essential to characterize their interactions with DNA. In the present report, we study the interactions of three types of f-CNTs, ammonium-functionalized single-walled and multiwalled carbon nanotubes (SWNT-NH3+; MWNT-NH3+), and lysine-functionalized single-walled carbon nanotubes (SWNT-Lys-NH3+), with plasmid DNA. Nanotube-DNA complexes were analyzed by scanning electron microscopy, surface plasmon resonance, PicoGreen dye exclusion, and agarose gel shift assay. The results indicate that all three types of cationic carbon nanotubes are able to condense DNA to varying degrees, indicating that both nanotube surface area and charge density are critical parameters that determine the interaction and electrostatic complex formation between f-CNTs with DNA. All three different f-CNT types in this study exhibited upregulation of marker gene expression over naked DNA using a mammalian (human) cell line. Differences in the levels of gene expression were correlated with the structural and biophysical data obtained for the f-CNT:DNA complexes to suggest that large surface area leading to very efficient DNA condensation is not necessary for effective gene transfer. However, it will require further investigation to determine whether the degree of binding and tight association between DNA and nanotubes is a desirable trait to increase gene expression efficiency in vitro or in vivo. This study constitutes the first thorough investigation into the physicochemical interactions between cationic functionalized carbon nanotubes and DNA toward construction of carbon nanotube-based gene transfer vector systems.     

A new type of entanglement involving one-dimensional ribbons of rings catenated to a three-dimensional network in the nanoporous structure of [Co(bix)2(H2O)2](SO4).7H2O [bix = 1,4-bis(imidazol-1-ylmethyl)benzene

Co(II) sulfate reacts with the flexible ligand 1,4-bis(imidazol-1-ylmethyl)benzene (bix) to yield the coordination network [Co(bix)2(H2O)2](SO4).7H2O, containing polymeric ribbons of rings which penetrate and catenate a 3D single frame of the CdSO4 topology, to produce an open-channel entangled architecture with nanoporous behaviour.