Volume 68, Issue 8

The gold(I) phosphinine complexes [AuCl(C 5 H 2 P-2,6-Me 2 -4-Ph)] and [AuCl(C 5 H 2 P-2,4,6-Ph 3 )] were prepared and structurally characterised by single-crystal X-ray diffraction studies. In the former case, individual molecules are aggregated in the crystal as crossed dimers with an Au···Au distance of 3:60 Å , compatible with a weak aurophilic interaction. In the latter case, intermolecular Au···π interactions involving the phosphinine ring are observed with Au···C distances in the range from ca. 3.32 to 3:44 Å , which make [AuCl(C 5 H 2 P-2,4,6-Ph 3 )] the first structurally characterised example of intermolecular Au···π interactions involving a heteroarene. Graphical Abstract Crystal Structures of the Gold(I) Phosphinine Complexes [AuCl(C 5 H 2 P-2,6-Me2-4-Ph)] and [AuCl(C 5 H 2 P-2,4,6-Ph 3 )]

We report the crystal structures of six diphosphane monochalcogenides [1: 1,2-bis(diphenylphosphano) methane sulfide (dppmS), 2: 1,2-bis(diphenylphosphano)ethane oxide (dppeO), 3: 1,2- bis(diphenylphosphano)ethane sulfide (dppeS), 4: 1,2-bis(diphenylphosphano)benzene sulfide (dppbzS), 5: 1,2-bis(diphenylphosphano)benzene selenide (dppbzSe), 6: 1,8-bis(diphenylphosphano)- naphthalene sulfide (dppnS) as its dichloromethane sesquisolvate and monosolvate 6a/6b]. No isotypy is observed for analogous compounds with the same phosphine but different chalcogens. The two independent molecules of 3 are superimposable to a good approximation up to and including the ipso carbons, but the ring orientations are different; 3 differs from 2 mainly by a rotation around the P1- C1 bond. The molecules of 4 and 5 are similar except for the disposition of the rings at P III . The two molecules of 6 show the distortions typical of 1,8-disubstituted naphthalenes and are closely similar. In the packing of structures 1-3 non-classical hydrogen bonds of the form C-H···E (E=chalcogen) are observed. In a supplement two supposedly new polymorphs of dppmSe 2 are shown to be probably identical to previously known forms. Graphical Abstract Phosphanchalkogenide und ihre Metallkomplexe. I. Strukturen einiger Diphosphanmonochalkogenide/ Phosphane Chalcogenides and their Metal Complexes. I. Structures of some Diphosphane Monochalcogenides

Single crystals of the high-pressure phase Ce 7 Au 13+x Ge 10-x were obtained by treating CeAuGe at 9:5 GPa and 1473 - 1523 K in a multi-anvil press. The structure of Ce 7 Au 13:35 Ge 9:65 was refined on the basis of single-crystal X-ray diffractometer data: new type, Pbam, a = 1571:9(3), b = 1780:3(4), c = 443:58(9) pm, wR2 = 0:0470, 2017 F 2 values, 96 variables. Two of the five germanium sites show a small degree of Ge/Au mixing. The gold and germanium atoms build up a complex threedimensional, covalently bonded [Au 13:35 Ge 9:65 ] network with Au-Ge distances ranging from 249 to 293 pm. The [Au 13:35 Ge 9:65 ] network also exhibits a one-dimensional gold cluster with Au-Au distances of 275 - 301 pm and a weakly bonded germanium dumb-bell with a Ge4-Ge5 bond length of 271 pm. The four crystallographically independent cerium atoms fill cavities of coordination numbers 19 and 20 within the [Au 13:35 Ge 9:65 ] network. These coordinations are known from other structure types. Consequently one can describe the Ce 7 Au 13:35 Ge 9:65 structure as an intergrowth variant of Eu- AuGe, HP-CeAuGe (TiNiSi), CeAu 2 Ge 2 (CePt 2 Ge 2 ), and Ce 3 Ag 4 Ge 4 (Gd 3 Cu 4 Sn 4 ) related slabs. Graphical Abstract One-dimensional Gold Clusters in HP-Ce 7 Au 13+x Ge 10–x

Reaction of MnSO 4 and trans-1,2-bis(4-pyridyl)ethene (bpe) results in a new coordination polymer, [Mn(H 2 O) 2 (bpe)(SO 4 )]·H 2 O. The title complex crystallizes in the polar monoclinic space group C2. The octahedrally coordinated Mn atoms are bridged by sulfate anions and bpe ligands to form two-dimensional sheets with (4 2 ·6 3 ·8) topology. This polar complex displays ferroelectricity with a remanent polarization (2P r ) of ca. 0:5779 μC cm -2 , a coercive field (2E c ) of 8:8 kV cm -1 , and a saturation of the spontaneous polarization (PS) of ca. 0:4177 μC cm -2 . The magnetic behavior of the title complex suggests significant antiferromagnetic coupling interactions between Mn(II) ions bridged by sulfate anions. Furthermore, the title complex was subjected to elemental analysis, IR spectroscopic measurement and thermal analysis. Graphical Abstract A Mn(II) Coordination Polymer with Sulfate and trans-1,2-Bis(4- pyridyl)ethylene Bridges: Synthesis, Structure, Magnetic and Ferroelectric Properties

New reaction conditions for the direct arylation of polyfluoroarenes with aryl iodides have been developed. This reaction can be co-catalyzed by palladium=copper without ligands and exhibits excellent functional group compatibility. Graphical Abstract Ligand-free Palladium/Copper Co-catalyzed Direct Arylation of Polyfluoroarenes with Aryl Iodides

The oxidation of methane to methanol takes place selectively by the photolysis of perrhenate in aqueous solution in the presence of methane. This photoreaction is formally an oxygen atom transfer. Because the reoxidation of the reduced perrhenate is accomplished with hydrogen peroxide the overall process can be viewed as photocatalytic oxidation of methane to methanol: CH 4 + H 2 O 2 → CH 3 OH+ H 2 O. Graphical Abstract Photooxidation of Methane to Methanol by Perrhenate in Water under Ambient Conditions

(E)-2-Chloro-3-(2-cyanovinyl)-9,10-dimethoxy-4-oxo-6,7-dihydro-4H-pyrido[2,1-a] isoquinoline- 1-carbonitrile (5) was obtained by treatment of the 2-chloro-3-formylpyrido[2,1-a]isoquinoline derivative 3 with 2-(triphenylphosphoranylidene)acetonitrile (4). Treatment of 5 with sodium azide afforded the corresponding azido compound 6 which could be reduced by sodium dithionite to compound 7. A novel isoquinolino[2,1-g][1,6]naphthyridine derivative 11 was obtained by the reaction of phenyl isothiocyanate with the phosphorane compound 8, which was prepared by the reaction of compound 6 with triphenylphosphine. Treatment of 5 with amines 12a-c and thiophenols 14a-c in refluxing ethanol afforded the corresponding substitution products 13a-c and 15a-c, respectively. Also, the reaction of 1 with a-oxo hydroxamoyl chlorides 16 was reinvestigated, and the synthesized pyrazoloisoquinolines 19a-f and pyridazinopyrazoloisoquinolines 20a, e were screened for their in vitro antitumor activities. Graphical Abstract A Novel Route to Isoquinoline[2,1-g][1,6]naphthyridine, Pyrazolo[5,1-a] isoquinoline and Pyridazino[4´,5´:3,4]pyrazolo[5,1-a]isoquinoline Derivatives With Evaluation of Antitumor Activities

The reactivity of N-amidinothiourea (1) as an electron donor towards several electron-accepting functional groups via electron-donor-acceptor (EDA) interaction has been studied. Thus on treatment of 1 with either 1,1,2,2-tetracyanoethylene (TCNE, 2), 2,3-dicyano-1,4-naphthoquinone (DCNQ, 4), 2,3,5,6-tetrabromo-1,4-benzoquinone (BHL-p, 6), 2,3-dichloro-1,4-naphthoquinone (DCHNQ, 8), 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL-p, 13), 2,3-dicyano-5,6-dichloro-1,4- benzoquinone (DDQ, 15), 2-dicyanomethyleneindan-1,3-dione (CNIND, 17), 2-(2-oxoindolin-3- ylidene)malononitrile (19), and/or dimethyl acetylenedicarboxylate (DMAD, 21), the reaction proceeds to give thiazole and thiazine derivatives, respectively. However, isoindole derivatives 24 and 26 were formed on heating of 1 with either tetrabromophthalic anhydride and=or o-phthalaldehyde, respectively. The products were fully characterized according to their spectral data. The mechanisms of formation of the products have been rationalized. Graphical Abstract Facile Synthesis of Thiazole, Thiazine and Isoindole Derivatives via EDA Approach and Conventional Methods

We report a conventional and simple method to synthesize quinazoline and benzodiazepine derivatives by treatment of 2-aminobenzylamine (1) with several p-electron-deficient compounds. Quinazoline derivatives were obtained by treatment of 1 with either tetracyanoethylene or 7,7,8,8-tetracyanoquinodimethane. Benzodiazepine derivatives were formed when 1 was reacted with either 2,3- dichloro-1,4-naphthoquinone or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. Fused quinazoline and benzoazepine derivatives were formed by dry heating of 1 with either naphthalic anhydride, cis- 1,2,3,6-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride and/or diphenic anhydride, respectively. The NMR spectra and the mass spectrometric data as well as elemental analyses of all new products are consistent with the proposed structures. The structures of the quinazoline derivatives 26 and 28 were further confirmed by single-crystal X-ray structure determination. Plausible mechanisms for the formation of several products are discussed. Graphical Abstract The Chemical and Structural Properties of 2-Aminobenzylamine Derivatives

Two new steroids, 22E, 24R-stigmast-22-ene-3,6,11-trione (1) and 22E, 24R-3-acetylstigmasta- 5,22-diene-7,11-dione (2), and one new ceramide, (2S,3S,4R,5R) N-(1,3,4,5-tetrahydroxyundecan- 2-yl)tetradecanamide (7), together with eleven known compounds were isolated from the CH 2 Cl 2 extract of the stem bark of Odyendyea gabonensis. The structures of all compounds were determined by comprehensive analyses of their 1D and 2D NMR, mass spectral (EI and ESI) data, chemical reactions, and comparison with previously known analogs. Pure compounds were tested for their activity against the bacteria Bacillus subtilis, Staphylococcus aureus and Escherichia coli, the fungi Mucor miehei and Candida albicans, and the plant pathogen oomycetes Aphanomyces cochlioides, Pythium ultimum and Rhizoctonia solani using the paper disk agar diffusion assay. For active compounds, MICs were determined by the broth microdilution assay. Cytotoxic activity against the human lung adenocarcinoma cell line A 549 was evaluated by the MTT assay. All compounds delivered low to missing antimicrobial activities in the agar diffusion assay and MICs > 1 μg mL -1 . The alkaloids 10 and 11 displayed cytotoxic activity against the human lung adenocarcinoma cell line A549 with IC 50 2.5 and 4:5 μm respectively. Graphical Abstract Steroids and Ceramide from the Stem Bark of Odyendyea gabonensis

A new bis-isoflavone derivative, named amphiisoflavone (1), was isolated from the roots of Amphimas pterocarpoides, together with three known isoflavones, namely 8-methoxyisoformononetin (2), 6-methoxyisoformononetin (3) and isoformononetin (4). Chemical transformations carried out on compound 3 led to two new derivatives, 4´-acetoxy-6,7-dimethylisoflavone (3a) and 4´-O-prenyl- 6,7-dimethylisoflavone (3p), along with a known compound, 4´,6,7-trimethoxyisoflavone (3m). The structures of all compounds were elucidated from spectroscopic evidence, in particular by 1D and 2D NMR spectroscopic methods. These compounds were evaluated for their antioxidant properties and for their antimicrobial activities against a wide range of bacteria and fungi. Graphical Abstract Antimicrobial and Antioxidant Isoflavonoid Derivatives from the Roots of Amphimas pterocarpoides

Two new poly-hydroxy steroids, zahramycins A (1) and B (2), have been isolated from the polar fraction of the extract of the coral Sarcophyton trocheliophorum. Compound 1 was confirmed to bear an oxirane ring at C-5 and C-6, while 2 has a keto-hydroxy sterol structure. The known DNA primary metabolites uracil, thymine, adenine, uridine, 2´-deoxyuridine, and thymidine were also isolated and identified. Structures of the new sterols 1 and 2 were confirmed by NMR ( 1 H, 13 C, 1 H- 1 H COSY, HMQC, HMBC, and NOESY) spectroscopy, mass spectrometry (EI, ESI, and HRMS), and by comparison with related structures. The antimicrobial and cytotoxic activities of compounds 1 and 2 along with that of the coral extract were also determined. Zahramycin B (2) showed high (15 mm) and moderate (12 mm) antibacterial activity against Staphylococcus aureus and Bacillus subtilis, and fungus Pythium ultimum (12 mm), while zahramycin A (1) and the crude extract of Sarcophyton trocheliophorum were inactive. Both steroids and the crude extract of Sarcophyton trocheliophorum showed no cytotoxicity. Graphical Abstract Zahramycins A-B, Two New Steroids from the Coral Sarcophyton trocheliophorum

Palladium nanoparticles supported on cellulose were prepared without using any reducing agent and used as a highly efficient catalyst for the Ullmann reductive coupling of aryl halides in the presence of zinc, in a water-alcohol mixture as solvent in air. The obtained palladium nanoparticles were characterized by scanning electron microscopy (SEM), FTIR, thermogravimetric analysis (TGA) and ICP-AES analysis. The synthesis of biaryls from chloroarenes was performed by this catalyst with good yield. The catalyst remains stable up to 75 °C and can be recovered and reused several times without loss of activity. Graphical Abstract Reductive Ullmann Coupling of Aryl Halides by Palladium Nanoparticles Supported on Cellulose, a Recoverable Heterogeneous Catalyst