-Bridged BODIPY Dimers: Exploring the Electron-Rich and Electron-Poor Coupling Limit via Pyrrole and Pyridine Annulation.

facile access to -heteroaryl-fused bis-BODIPY scaffolds has been developed. A BODIPY dimer with an α,α-amine linker serves as a starting material to obtain pyrrole- and pyridine-fused BODIPYs, either by direct oxidation or by oxidative condensation with an aldehyde building block. Both species mark antipodal conjugative coupling conditions that result in distinct spectral outcomes.

Novel Tricyclic Flavonoids as Promising Anti-MRSA Agents.

Methicillin-resistant (MRSA) is considered the main cause of nosocomial and community-associated infections. Because of antimicrobial resistance, MRSA infections are difficult or impossible to treat, leading to high mortality rates and significant economic and societal costs. In view of the MRSA challenge to public health all over the world, the identification of new and effective anti-MRSA agents is a high medical priority.

Crystal structures of seven mixed-valence gold compounds of the form [( P)Au][Au ] ( = -butyl or isopropyl, = S or Se, and = Cl or Br).

During our studies of the oxidation of gold(I) complexes of tri-alkyl-phosphane chalcogenides, general formula PAu, ( = -butyl or isopropyl, = S or Se, = Cl or Br) with PhICl or elemental bromine, we have isolated a set of seven mixed-valence by-products, the bis-(tri-alkyl-phosphane chalcogenido)gold(I) tetra-halogenidoaurates(III) [( P)Au][Au ]. These corres-pond to the addition of one halogen atom per gold atom of the Au precursor. Com-pound , bis-(triiso-propyl-phosphane sulfide)-gold(I) tetra-chlorido-aur-ate(III), [Au(CHPS)][AuCl] or [( PrPS)Au][AuCl], crystallizes in space group 2/ with = 4; the gold(I) atoms of the two cations lie on twofold rotation axes, and the gold(III) atoms of the two anions lie on inversion centres.

Synthesis and Reactivity of Dipalladated Derivatives of Terephthalaldehyde.

The polynuclear complex [{μ-1,4,,″-CH{C(H)=N(Bu)}-2,5}{Pd(μ-OAc)}] () reacts with tbbpy (4,4'-di--butyl-2,2'-bipyridine) and TlOTf to form the dinuclear complex [{μ-1,4,,″-CH{C(H)=N(Bu)}-2,5}{Pd(tbbpy)}] (). The hydrolysis of with acetic acid in a 5:1 acetone/water mixture, in the presence of two equivalents of tbbpy and excess NaX (X = Br, I), yields the dipalladated terephthalaldehyde complexes [CH{PdX(tbbpy)}-1,4-(CHO)-2,5] [X = Br (), X = I ()], which are the first fully characterized complexes of this type. The reaction of with CO results in the insertion of CO into both aryl-Pd bonds, forming [CH{C(O){PdX(tbbpy)}}-1,4-(CHO)-2,5] [X = Br (), X = I ()], which are the first examples of complexes with CO inserted into two separate aryl-metal bonds involving the same ligand.

Crystal structures of seven gold(III) complexes of the form Au ( = substituted pyridine, = Cl or Br).

The structures of seven gold(III) halide derivatives of general formula Au ( = methyl-pyridines or di-methyl-pyridines, = Cl or Br) are presented: tri-chlorido-(2-methyl-pyridine)-gold(III), [AuCl(CHN)], (as two polymorphs and ); tri-bromido-(2-methyl-pyridine)-gold(III), [AuBr(CHN)], ; tri-bromido-(3-methyl-pyridine)-gold(III), [AuBr(CHN)], ; tri-bromido-(2,4-di-meth-yl-pyridine)-gold(III), [AuBr(CHN)], ; tri-chlorido-(3,5-di-methylpyridine)-gold(III), [AuCl(CHN)], ; tri-bromido-(3,5-di-methyl-pyridine)-gold(III), [AuBr(CHN)], , and tri-chlorido-(2,6-di-methyl-pyridine)-gold(III), [AuCl(CHN)], . Additionally, the structure of , the 1:1 adduct of and , [AuBr(CHN)]·[AuBr(CHN)], is included. All the structures crystallize solvent-free, and all have ' = 1 except for and , which display crystallographic twofold rotation symmetry, and , which has ' = 2.

Crystal structures of four thio-glycosides involving carbamimido-thio-ate groups.

The compounds 2',3',4',6'-tetra--acetyl-β-d-gluco-pyranosyl '-cyano--phenyl-carbamimido-thio-ate (CHNOS, ), 2',3',4',6'-tetra--acetyl-β-d-galacto-pyranosyl '-cyano-phenyl-carbamimido-thio-ate, (CHNOS, ), 2',3',4',6'-tetra--acetyl-β-d-galacto-pyranosyl '-cyano--methyl-carbamimido-thio-ate (CHNOS, ), and 2',3',4',6'-tetra--acetyl-β-d-galacto-pyranosyl '-cyano---tolyl-carbamimido-thio-ate (CHNOS, ) all crystallize in 222 with = 4. For all four structures, the configuration across the central (formal) C=N(CN) double bond of the carbamimido-thio-ate group is . The torsion angles C5-O1-C1-S (standard sugar numbering) are all close to 180°, confirming the β position of the substituent.

Crystal structures of four gold(I) complexes [Au ][Au ] and a by-product (·H)[AuBr] ( = substituted pyridine, = Cl or Br).

Bis(2-methyl-pyridine)-gold(I) di-bromido-aurate(I), [Au(CHN)][AuBr], (), crystallizes in space group 2/ with = 4. Both gold atoms lie on twofold axes and are connected by an aurophilic contact. A second aurophilic contact leads to infinite chains of alternating cations and anions parallel to the axis, and the residues are further connected by a short H⋯Au contact and a borderline Br⋯Br contact.

Crystal structures of tri-chlorido-(4-methyl-piperidine)gold(III) and two polymorphs of tri-bromido(4-methyl-piperidine)-gold(III).

Tri-chlorido-(4-methyl-piperidine)-gold(III), [AuCl(CHN)], , crystallizes in with = 8. Tri-bromido-(4-methyl-piperidine)-gold(III), [AuBr(CHN)], , crystallizes as two polymorphs, in with = 4 (imposed mirror symmetry) and , which is isotypic to . The Au-N bonds to Cl are somewhat shorter than those to Br, and the Au-Cl bonds to N are longer than those to N, whereas the Au-Br bonds to N are slightly shorter than the bonds.

Crystal structure of ()--(4-bromo-phen-yl)-2-cyano-3-[3-(2-methyl-prop-yl)-1-phenyl-1-pyrazol-4-yl]prop-2-enamide.

The structure of the title compound, CHBrNO, contains two independent mol-ecules connected by hydrogen bonds of the type N-H⋯N≡C to form a dimer. The configuration at the exocyclic C=C double bond is . The mol-ecules are roughly planar except for the isopropyl groups.

Crystal structures of fourteen halochalcogenylphos-pho-nium tetra-halogenidoaurates(III).

The structures of fourteen halochalcogenyl-phospho-nium tetra-halogen-ido-aurates(III), phosphane chalcogenide derivatives with general formula [ P][Au ] ( = -butyl; = isopropyl; = 0 to 3; = S or Se; = Cl or Br) are presented. The eight possible chlorido derivatives are: , = 3, = S; , = 2, = S; , = 1, = S; , = 0, = S; , = 3, = Se; , = 2, = Se; , = 1, = Se; and , = 0, = Se, and the corresponding bromido derivatives are - in the same order. Structures were obtained for all compounds except for the tri--butyl derivatives and .

Silver Organometallics that are Highly Potent Thioredoxin and Glutathione Reductase Inhibitors: Exploring the Correlations of Solution Chemistry with the Strong Antibacterial Effects.

The antibacterial activity of silver species is well-established; however, their mechanism of action has not been adequately explored. Furthermore, issues of low-molecular silver compounds with cytotoxicity, stability, and solubility hamper their progress to drug leads. We have investigated silver N-heterocyclic carbene (NHC) halido complexes [(NHC)AgX, X = Cl, Br, and I] as a promising new type of antibacterial silver organometallics.

Crystal structures of ten phosphane chalcogenide complexes of gold(III) chloride and bromide.

The structures of ten phosphane chalcogenide complexes of gold(III) halides, with general formula PAu ( = -butyl; = -propyl; = 0 to 3; = S or Se; = Cl or Br) are presented. The eight possible chlorido derivatives are: , = 3, = S; , = 2, = S; , = 1, = S; , = 0, = S; , = 3, = Se; , = 2, = Se; , = 1, = Se; and , = 0, = Se, and the corresponding bromido derivatives are - in the same order. Structures were obtained for , (and a second polymorph ), (and its deutero-chloro-form monosolvate ), (as its di-chloro-methane monosolvate), , (as its deutero-chloro-form monosolvate , in which the solvent mol-ecule is disordered over two positions), , , and .

Crystal structure of 2,4-di-amino-5-(4-hy-droxy-3-meth-oxy-phen-yl)-8,8-dimethyl-6-oxo-6,7,8,9-tetra-hydro-5-chromeno[2,3-]pyridine-3-carbo-nitrile-di-methyl-formamide-water (1/1/1).

In the structure of the title compound, CHNO·CHNO·HO, the entire tricyclic system is approximately planar except for the carbon atom bearing the two methyl groups; the meth-oxy-phenyl ring is approximately perpendicular to the tricycle. All seven potential hydrogen-bond donors take part in classical hydrogen bonds. The main mol-ecule and the DMF combine to form broad ribbons parallel to the axis and roughly parallel to the plane; the water mol-ecules connect the residues in the third dimension.

Linear Amine-Linked Oligo-BODIPYs: Convergent Access via Buchwald-Hartwig Coupling.

A convergent route toward nitrogen-bridged BODIPY oligomers has been developed. The synthetic key step is a Buchwald-Hartwig cross-coupling reaction of an α-amino-BODIPY and the respective halide. Not only does the selective synthesis provide control of the oligomer size, but the facile preparative procedure also enables easy access to these types of dyes.

Crystal structure of 4-(benzo[]thia-zol-2-yl)-1,2-dimethyl-1-pyrazol-3(2)-one.

In the title compound, CHNOS, the inter-planar angle between the pyrazole and benzo-thia-zole rings is 3.31 (7)°. In the three-dimensional mol-ecular packing, the carbonyl oxygen acts as acceptor to four C-H donors (with one H⋯O as short as 2.

Crystal structures of five gold(I) complexes with methyl-piperidine ligands.

In bis-(4-methyl-piperidine-κ)gold(I) chloride, [Au(CHN)]Cl (), the methyl groups are, as expected, equatorial at the piperidine ring, but the Au atom is axial; this is the case for all five structures reported here, as is the expected linear coordination at the Au atom. Hydrogen bonding of the form N-H⋯Cl⋯H-N leads to inversion-symmetric dimers, which are further connected by C-H⋯Au contacts. Bis(4-methyl-piperidine-κ)gold(I) di-chlorido-aurate(I), [Au(CHN)][AuCl] (), also forms inversion-symmetric dimers; these involve aurophilic inter-actions and three-centre hydrogen bonds of the form NH(⋯Cl).

An unexpected tautomer: synthesis and crystal structure of -[6-amino-4-(methyl-sulfan-yl)-1,2-di-hydro-1,3,5-triazin-2-yl-idene]benzenesulfonamide.

The title compound, CHNOS, consists of an unexpected tautomer with a protonated nitro-gen atom in the triazine ring and a formal exocyclic double bond C=N to the sulfonamide moiety. The ring angles at the unsubstituted nitro-gen atoms are narrow, at 115.57 (12) and 115.

Crystal structures of the isotypic complexes bis-(morpholine)-gold(I) chloride and bis-(morpholine)-gold(I) bromide.

The compounds bis-(morpholine-κ)gold(I) chloride, [Au(CHNO)]Cl, , and bis-(morpholine-κ)gold(I) bromide, [Au(CHNO)]Br, , crystallize isotypically in space group 2/ with = 4. The gold atoms, which are axially positioned at the morpholine rings, lie on inversion centres (so that the N-Au-N coordination is exactly linear) and the halide anions on twofold axes. The residues are connected by a classical hydrogen bond N-H⋯halide and by a short gold⋯halide contact to form a layer structure parallel to the plane.

Crystal structures of sixteen phosphane chalcogenide complexes of gold(I) chloride, bromide and iodide.

The structures of 16 phosphane chalcogenide complexes of gold(I) halides, with the general formula PAu ( = -butyl; = isopropyl; = 0 to 3; = S or Se; = Cl, Br or I), are presented. The eight possible chlorido derivatives are: , = 3, = S; , = 2, = S; , = 1, = S; , = 0, = S; , = 3, = Se; , = 2, = Se; , = 1, = Se; and , = 0, = Se, and the corresponding bromido derivatives are - in the same order. However, and were badly disordered and was not obtained.

Crystal structure of 2-[(5-amino-1-tosyl-1-pyrazol-3-yl)-oxy]-1-(4-meth-oxy-phen-yl)ethan-1-one 1,4-dioxane monosolvate.

In the structure of the title compound, CHNOS·CHO, the two independent dioxane mol-ecules each display inversion symmetry. The pyrazole ring is approximately parallel to the aromatic ring of the oxy-ethanone group and approximately perpendicular to the tolyl ring of the sulfonyl substituent. An extensive system of classical and 'weak' hydrogen bonds connects the residues to form a layer structure parallel to (201), within which dimeric subunits are conspicuous; neighbouring layers are connected by classical hydrogen bonds to dioxanes and by 'weak' hydrogen bonds from H donors.

Emergency department crowding is not being caused by increased inappropriate presentations.

Contrary to the prevailing wisdom, there may be little or no room to move with respect to reducing emergency department (ED) utilisation, as ED utilisation in Aotearoa New Zealand is low by world standards and is not driven by patients presenting inappropriately with minor conditions. We should continue the excellent work done in the primary care sector to maintain our low ED presentation rate and support primary and urgent care providers to provide alternatives to the ED for people with minor conditions. However, to reduce the system pressure and harms caused by ED crowding due to access block for admitted patients, we also need to adequately resource our hospital-based inpatient teams and EDs so that the (appropriate) acute care workload can be managed safely.

Access to isoindole-derived BODIPYs by an aminopalladation cascade.

Here, we present a new route to dyes of the BODIPY family. We first built up a -Boc-protected dipyrromethene scaffold an aminopalladation cascade. Subsequentially, the pyrrole moiety was deprotected and the BF unit inserted.

Synthesis of the indeno[1,2-]indole core of janthitrem B.

The tetracyclic core structure of the majority of indole diterpenoids features a -hydrindane moiety that is fused to an indole unit. We report here a novel synthetic route that includes a photo-Nazarov cyclization of a 3-acylindole precursor initially providing the thermodynamically preferred -hydrindanone. After reduction and conversion to the cyclopentadiene, dihydroxylation and hydrogenation provided the indoline.

Crystal structures of five halido gold complexes involving piperidine or pyrrolidine as ligands or (protonated) as cations.

In bromido-(pyrrolidine-κ)gold(I) bis-(pyrrolidine-κ)gold(I) bromide, [AuBr(pyr)]·[Au(pyr)]Br (pyr = pyrrolidine, CHN), , alternating [AuBr(pyr)] mol-ecules and [Au(pyr)] cations are connected by aurophilic contacts to form infinite chains of residues parallel to the axis. The chains are cross-linked by three N-H⋯Br hydrogen bonds and an Au⋯Br contact to form a layer structure parallel to the plane. Tri-chlorido-(piperidine-κ)gold(III), [AuCl(pip)] (pip = piperidine, CHN), , consists of mol-ecules with the expected square-planar coordination at the gold atom, which are connected by an N-H⋯Cl hydrogen bond and an Au⋯Cl contact to form a layer structure parallel to the plane.

Crystal structure of 2-{[5-(methyl-sulfan-yl)-4-phenyl-4-1,2,4-triazol-3-yl]meth-yl}benzo[]thia-zole.

In the structure of the title compound, CHNO, the triazole ring exhibits inter-planar angles of 63.86 (2) and 76.96 (2)° with the phenyl and benzo-thia-zole planes, respectively.