Ultrathin Hexagonal Hybrid Nanosheets Synthesized by Graphene Oxide‐Assisted Exfoliation of β‐Co(OH)2 Mesocrystals

In the present study, we report the synthesis of a high‐quality, single‐crystal hexagonal β‐Co(OH)₂ nanosheet, exhibiting a thickness down to ten atomic layers and an aspect ratio exceeding 900, by using graphene oxide (GO) as an exfoliant of β‐Co(OH)₂ nanoflowers. Unlike conventional approaches using ionic precursors in which morphological control is realized by structure‐directing molecules, the β‐Co(OH)₂ flower‐like superstructures were first grown by a nanoparticle‐mediated crystallization process, which results in large 3D superstructure consisting of ultrathin nanosheets interspaced by polydimethoxyaniline (PDMA). Thereafter, β‐Co(OH)₂ nanoflowers were chemically exfoliated by surface‐active GO under hydrothermal conditions into unilamellar single‐crystal nanosheets. In this reaction, GO acts as a two‐dimensional (2D) amphiphile to facilitate the exfoliation process through tailored interactions between organic and inorganic molecules. Meanwhile, the on‐site conjugation of GO and Co(OH)₂ promotes the thermodynamic stability of freestanding ultrathin nanosheets and restrains further growth through Oswald ripening. The unique 2D structure combined with functionalities of the hybrid ultrathin Co(OH)₂ nanosheets on rGO resulted in a remarkably enhanced lithium‐ion storage performance as anode materials, maintaining a reversible capacity of 860 mA h g^?1 for as many as 30 cycles. Since mesocrystals are ubiquitous and rich in morphological diversity, the strategy of the GO‐assisted exfoliation of mesocrystals developed here provides an opportunity for the synthesis of new functional nanostructures that could bear importance in clean renewable energy, catalysis, photoelectronics, and photonics.     

Synthesis and Characterization of β‐Co(OH)2, CuO and ZnO Nanostructures by Solvothermal Method without Any Additive

β‐Co(OH)₂, CuO and ZnO nanostructures with plate‐like, particle‐like and flower‐like morphologies were prepared through the use of simple solvothermal method using of melt salt and 1,10‐phenanthroline as complexing agent and sodium hydroxide. β‐Co(OH)₂ consisted of a plate‐like structure, and the nanoplates size was about 29 nm. The structure was comprised of regular sheets which were assembled together. Furthermore, the as‐obtained β‐Co(OH)₂ nanoplates can be easily converted into Co₃O₄ nanoplates by calcining in air at 500 °C for 2 h. The results indicate that ZnO powder is of hexagonal wurtzite structure and well crystallized with high purity. CuO powder is pure monoclinic‐structured crystalline. The products were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared (FT‐IR) spectra. Possible formation mechanism of the nanostructures is proposed.     

A two‐dimensional ZnII coordination polymer constructed from benzene‐1,2,3‐tricarboxylic acid and N,N′‐bis[(pyridin‐4‐yl)methylidene]hydrazine

The hydrothermal synthesis of the novel complex poly[aqua(μ₄‐benzene‐1,2,3‐tricarboxylato)[μ₂‐4,4′‐(hydrazine‐1,2‐diylidenedimethanylylidene)dipyridine](μ₃‐hydroxido)dizinc(II)], [Zn(C₉H₃O₆)(OH)(C₁₂H₁₀N₄)(H₂O)]_n, is described. The benzene‐1,2,3‐tricarboxylate ligand connects neighbouring Zn₄(OH)₂ secondary building units (SBUs) producing an infinite one‐dimensional chain. Adjacent one‐dimensional chains are connected by the N,N′‐bis[(pyridin‐4‐yl)methylidene]hydrazine ligand, forming a two‐dimensional layered structure. Adjacent layers are stacked to generate a three‐dimensional supramolecular architecture via O—H...O hydrogen‐bond interactions. The thermal stability of this complex is described and the complex also appears to have potential for application as a luminescent material.     

Structure‐Dependent Electrocatalysis of Ni(OH)2 Hourglass‐like Nanostructures Towards L‐Histidine

As the properties of nanomaterials are strongly dependent on their size, shape and nanostructures, probing the relations between macro‐properties and nanostructures is challenging for nanoscientists. Herein, we deliberately chose three types of Ni(OH)₂ with hexagonal, truncated trigonal, and trigonal hourglass‐like nanostructures, respectively, as the electrode modifier to demonstrate the correlation between the nanostructures and their electrocatalytic performance towards L ‐histidine. It was found that the hexagonal hourglass‐like Ni(OH)₂ sample had the best electrocatalytic activity, which can be understood by a cooperative mechanism: on one hand, the hexagonal sample possesses the largest specific surface area and the tidiest nanostructure, resulting in the most orderly packing on the electrode surface; on the other hand, its internal structure with the most stacking faults would generate a lot of unstable protons, leading to an enhanced electronic conductivity. The findings are important because they provide a clue for materials design and engineering to meet a specific requirement for electrocatalysis of L ‐histidine, possibly even for other biomolecules. In addition, the hexagonal Ni(OH)₂‐based biosensor shows excellent sensitivity and selectivity in the determination of L ‐histidine and offers a promising feature for the analytical application in real biological samples.     

1‐(β‐d‐Erythrofuranos­yl)cytidine (β‐erythrocytidine)

1‐(β‐d ‐Erythrofuranosyl)cytidine, C₈H₁₁N₃O₄, (I), a derivative of β‐cytidine, (II), lacks an exocyclic hydroxy­methyl (–CH₂OH) substituent at C4′ and crystallizes in a global conformation different from that observed for (II). In (I), the β‐d ‐erythrofuranosyl ring assumes an E₃ conformation (C3′‐exo; S, i.e. south), and the N‐glycoside bond conformation is syn. In contrast, (II) contains a β‐d ‐ribofuranosyl ring in a ³T₂ conformation (N, i.e. north) and an anti‐N‐glycoside linkage. These crystallographic properties mimic those found in aqueous solution by NMR with respect to furan­ose conformation. Removal of the –CH₂OH group thus affects the global conformation of the aldofuranosyl ring. These results provide further support for S/syn–anti and N/anti correlations in pyrimidine nucleosides. The crystal structure of (I) was determined at 200 K.     

β‐Co(OH)2 Nanosheets: A Superior Pseudocapacitive Electrode for High‐Energy Supercapacitors

In this work, β‐Co(OH)₂ nanosheets are explored as efficient pseudocapacitive materials for the fabrication of 1.6 V class high‐energy supercapacitors in asymmetric fashion. The as‐synthesized β‐Co(OH)₂ nanosheets displayed an excellent electrochemical performance owing to their unique structure, morphology, and reversible reaction kinetics (fast faradic reaction) in both the three‐electrode and asymmetric configuration (with activated carbon, AC). For example, in the three‐electrode set‐up, β‐Co(OH)₂ exhibits a high specific capacitance of ∼675 F g⁻¹ at a scan rate of 1 mV s⁻¹. In the asymmetric supercapacitor, the β‐Co(OH)₂∥AC cell delivers a maximum energy density of 37.3 Wh kg⁻¹ at a power density of 800 W kg⁻¹. Even at harsh conditions (8 kW kg⁻¹), an energy density of 15.64 Wh kg⁻¹ is registered for the β‐Co(OH)₂∥AC assembly. Such an impressive performance of β‐Co(OH)₂ nanosheets in the asymmetric configuration reveals the emergence of pseudocapacitive electrodes towards the fabrication of high‐energy electrochemical charge storage systems.     

Bis{2‐[(phenylimino)ethyl]‐1H‐pyrrol‐1‐ido‐κ2N,N′}nickel(II): a supramolecular structure formed by C—H...π hydrogen bonds

In the title compound, [Ni(C₁₂H₁₁N₂)₂], the Ni^II cation lies on an inversion centre and has a square‐planar coordination geometry. This transition metal complex is composed of two deprotonated N,N′‐bidentate 2‐[(phenylimino)ethyl]‐1H‐pyrrol‐1‐ide ligands around a central Ni^II cation, with the pyrrolide rings and imine groups lying trans to each other. The Ni—N bond lengths range from 1.894 (3) to 1.939 (2) Å and the bite angle is 83.13 (11)°. The Ni—N(pyrrolide) bond is substantially shorter than the Ni—N(imino) bond. The planes of the phenyl rings make a dihedral angle of 78.79 (9)° with respect to the central NiN₄ plane. The molecules are linked into simple chains by an intermolecular C—H...π interaction involving a phenyl β‐C atom as donor. Intramolecular C—H...π interactions are also present.     

Generalized Low‐Temperature Fabrication of Scalable Multi‐Type Two‐Dimensional Nanosheets with a Green Soft Template

Two‐dimensional nanosheets with high specific surface areas and fascinating physical and chemical properties have attracted tremendous interests because of their promising potentials in both fundamental research and practical applications. However, the problem of developing a universal strategy with a facile and cost‐effective synthesis process for multi‐type ultrathin 2 D nanostructures remains unresolved. Herein, we report a generalized low‐temperature fabrication of scalable multi‐type 2 D nanosheets including metal hydroxides (such as Ni(OH)₂, Co(OH)₂, Cd(OH)₂, and Mg(OH)₂), metal oxides (such as ZnO and Mn₃O₄), and layered mixed transition‐metal hydroxides (Ni‐Co LDH, Ni‐Fe LDH, Co‐Fe LDH, and Ni‐Co‐Fe layered ternary hydroxides) through the rational employment of a green soft‐template. The synthesized crystalline inorganic nanosheets possess confined thickness, resulting in ultrahigh surface atom ratios and chemically reactive facets. Upon evaluation as electrode materials for pseudocapacitors, the Ni‐Co LDH nanosheets exhibit a high specific capacitance of 1087 F g^?1 at a current density of 1 A g^?1, and excellent stability, with 103 % retention after 500 cycles. This strategy is facile and scalable for the production of high‐quality ultrathin crystalline inorganic nanosheets, with the possibility of extension to the preparation of other complex nanosheets.     

An Imidazoline–Aminophenol (IAP) Nickel Catalyst: Structure and Catalytic Activity in the Enantioselective 1,4‐Addition of 3′‐Indolyl‐3‐Oxindoles to Nitroethylene

The structure of a nickel complex of imidazoline–aminophenol (IAP) prepared from IAP with Ni(OAc)₂ was elucidated as cis‐bis(imidazolineaminophenoxide) [Ni(IAP)₂]. The [Ni(IAP)₂] complex smoothly promoted catalytic asymmetric 1,4‐addition of 3′‐indolyl‐3‐oxindole to nitroethylene to provide chiral mixed 3,3′‐bisindoles with high enantioselectivities. Mechanistic studies using ESI‐MS analyses suggest that one IAP ligand dissociated from [Ni(IAP)₂] to generate the Ni–enolate of 3′‐indolyl‐3‐oxindole. From the optically active 3,3′‐mixed indole adduct, biologically important 3′‐indolyl‐3‐pyrrolidinoindoline was successfully synthesized in a three‐step reaction sequence.     

Tetraaqua(4,4′‐dimethyl‐2,2′‐bipyridine‐κ2N,N′)nickel(II) sulfate monohydrate: a simple molecule with an extremely complex hydrogen‐bonding scheme

The title ionic compound, [Ni(C₁₂H₁₂N₂)(H₂O)₄]SO₄·H₂O, is composed of an Ni^II cation coordinated by a chelating 4,4′‐dimethyl‐2,2′‐bipyridine ligand via its two N atoms [mean Ni—N = 2.056 (2) Å] and by four aqua ligands [mean Ni—O = 2.073 (9) Å], the net charge being balanced by an external sulfate anion. The whole structure is stabilized by a solvent water molecule. Even though the individual constituents are rather featureless, they generate an extremely complex supramolecular structure consisting of a central hydrogen‐bonded two‐dimensional hydrophilic nucleus made up of complex cations, sulfate anions and coordinated and solvent water molecules, with pendant hydrophobic 4,4′‐dimethyl‐2,2′‐bipyridine ligands which interact laterally with their neighbours viaπ–π interactions. The structure is compared with closely related analogues in the literature.     

Mononuclear Carbene Dithiolate [Ni(NHX)(′S2C ′)] Complexes with HNX = HNPiPr3 or HNSPh2 Coligands (′S2C ′ 2– = 1,3‐ImidazolidinylN,N′‐bis(2‐benzenethiolate)(2–))

Cleavage reactions of the dinuclear [{Ni(′S₂C ′)}₂] · DMF (′S₂C ′ ^2– = 1,3‐imidazolidinyl‐N,N′‐bis(2‐benzenethiolate)(2–)) with HNPiPr₃ or HNSPh₂ yielded the mononuclear complexes [Ni(NHPiPr₃)(′S₂C ′)] ( 1 ) and [Ni(NHSPh₂)(′S₂C ′)] ( 2 ) which have been completely characterized. The nickel‐carbene‐dithiolate [Ni(′S₂C ′)] moiety is one of the very rare complex fragments that are able to coordinate both HNPR₃ or HNSR₂. IR spectra and X‐ray structure determinations show that 1 and 2 exhibit intramolecular N–H…S(thiolate) hydrogen bonds. Geometric parameters and NMR spectroscopic data of 1 and 2 are compatible with N–X single bonds and ylidic structures of the HNPiPr₃ and HNSPh₂ ligands. Comparison of Ni–N distances in diamagnetic and paramagnetic [Ni(NHSPh₂)] complexes was rendered possible through the X‐ray structure determination of the homoleptic [Ni(NHSPh₂)₆]Cl₂ ( 3 ) which formed as minor by‐product in the synthesis of 2 .     

Disorder and conformational analysis of methyl β‐d‐galactopyranosyl‐(1→4)‐β‐d‐xylopyranoside

Methyl β‐d ‐galactopyranosyl‐(1→4)‐β‐d ‐xylopyranoside, C₁₂H₂₂O₁₀, (II), crystallizes as colorless needles from water with positional disorder in the xylopyranosyl (Xyl) ring and no water molecules in the unit cell. The internal glycosidic linkage conformation in (II) is characterized by a ϕ′ torsion angle (C2′_Gal—C1′_Gal—O1′_Gal—C4_Xyl) of 156.4 (5)° and a ψ′ torsion angle (C1′_Gal—O1′_Gal—C4_Xyl—C3_Xyl) of 94.0 (11)°, where the ring atom numbering conforms to the convention in which C1 denotes the anomeric C atom, and C5 and C6 denote the hydroxymethyl (–CH₂OH) C atoms in the β‐Xyl and β‐Gal residues, respectively. By comparison, the internal linkage conformation in the crystal structure of the structurally related disaccharide, methyl β‐lactoside [methyl β‐d ‐galactopyranosyl‐(1→4)‐β‐d ‐glucopyranoside], (III) [Stenutz, Shang & Serianni (1999). Acta Cryst. C 55 , 1719–1721], is characterized by ϕ′ = 153.8 (2)° and ψ′ = 78.4 (2)°. A comparison of β‐(1→4)‐linked disaccharides shows considerable variability in both ϕ′ and ψ′, with the range in the latter (∼38°) greater than that in the former (∼28°). Inter‐residue hydrogen bonding is observed between atoms O3_Xyl and O5′_Gal in the crystal structure of (II), analogous to the inter‐residue hydrogen bond detected between atoms O3_Glc and O5′_Gal in (III). The exocyclic hydroxymethyl conformations in the Gal residues of (II) and (III) are identical (gauche–trans conformer).     

Synthetic and Structural Studies on Copper 1 H‐[1,10]‐Phenanthrolin‐2‐one Coordination Complexes: Isolation of a Novel Intermediate During 1,10‐Phenanthroline Hydroxylation

The synthesis and crystal structure elucidation of a novel dinuclear heteroleptic copper(II) complex has led to an alternative mechanism in the formation of covalent hydrates. During further studies on the synthesis and properties of [Cu₂(ophen)₂] ( 1 ), a dinuclear complex of copper(I) with 1 H‐[1,10]‐phenanthrolin‐2‐one (Hophen), two intermediates/alternative products 2 and 3 were isolated. The dinuclear, antiferromagnetic complex [Cu₂(ophen)₂(phen)₂] ? (NO₃)₂ ? 9H₂O ( 3 , phen=1,10‐phenanthroline) contains two five‐coordinate copper(II) ions, both with trigonal‐bipyramidal coordination, which are bridged together through deprotonated hydroxyl groups with a Cu? Cu non‐bonding distance of 3.100 Å. Complex [Cu(phen)₂(H₂O)] ? (NO₃)₂ ( 2 ) is a polymorph of a previously reported material. The occurrence of 2 and 3 has led us to propose a variation to the Gillard mechanism for the formation of covalent hydrates in bidentate N‐heterocycles in which the attacking nucleophile may be the deprotonated form of 2 , [Cu(phen)₂(OH)]^?, rather than free OH^?.     

Synthesis of β‐Arylacyl/β‐Heteroarylacyl‐β‐alkylidene Malonates and Their Application in Substituted Pyridone Synthesis

A novel approach has been developed for the synthesis of β‐arylacyl/β‐heteroarylacyl‐β‐alkylidine malonates in moderate to good yields by the reaction of Stork aryl and heteroaryl enamine with β‐chloroalkylidene malonates. The reaction involves conjugate (Michael) addition of Stork enamine on β‐chloroalkylidene malonates and elimination of chloride ion. These Michael adducts were utilized as intermediates for the synthesis of highly substituted 1,4‐dialkyl‐2‐oxo‐6‐aryl/hetreoaryl‐1,2‐dihydro‐pyridine‐3‐carboxylic acid ethyl esters via 5 + 1 ring annulation protocol.     

Structure of tetra[β‐(1,2,4‐triazole‐l‐yl) propiophenone] dichloro nickel(II) solvate hexahydrate complex: [NiCl2(C2H2N3CH2CH2‐COPh)4]·6H2O

The mononuclear complex, [NiCl₂ (trzCH₂CH₂COPh)₄]·6H₂O (trz =1,2,4‐triazole), was synthesized and its structure was determined by single crystal X‐ray determination. It crystallizes in the monoclinic system, space group P2₁/c, with lattice parameters: a = 0.80391(2) nm, b = 1.08215(2) tun, c = 2.90133(2) nm, β = 94.792 (1)° and Z = 2. Each nickel atom is coordinated by four N atoms of triazole from four β‐(1,2,4‐triazole‐1‐yl)propiophenone ligands and two chloride anions in trans arrangement with octahedral coordination geometry. In addition to the coordinating nickel complex, there are six uncoordinated water molecules. The Ni‐Cl distance is 0.24865(8) nm and the Ni‐N distances are in the range of 0.2072(2) to 0.2099(2) nm, respectively. In the solid state, the title compound forms three dimensional network structure through hydrogen bonds. The intermolecular hydrogen bonds connect the [NiCl₂(C₂H₂N₃CH₂CH₂COPh)₄] and H₂O moieties. The deep green crystals were also examined by elemental analysis, FT‐IR and UV spectra, which are in agreement with the structural data.     

Supramolecular inclusion complexes of a star polymer containing cholesterol end‐capped poly(ε‐caprolactone) arms with β‐cyclodextrin

A novel hexa‐armed and star‐shaped polymer containing cholesterol end‐capped poly(ε‐caprolactone) arms emanating from a phosphazene core (N₃P₃‐(PCL‐Chol)₆) was synthesized by a combination of ring‐opening polymerization and “click” chemistry techniques. For this purpose, the terminal ? OH groups of the synthesized precursor (N₃P₃‐(PCL‐OH)₆) were converted into –Chol through a series of reaction. Both N₃P₃‐(PCL‐OH)₆ and N₃P₃‐(PCL‐Chol)₆ were then employed in the preparation of supramolecular inclusion complexes (ICs) with β‐cyclodextrin (β‐CD). The latter formed ICs with β‐CD in higher yield. The host–guest stoichiometry (ε‐CL:β‐CD, mol:mol) in the ICs of N₃P₃‐(PCL‐Chol)₆ was found to be 1.2. The formation of supramolecular ICs of N₃P₃‐(PCL‐Chol)₆ with β‐CD was confirmed by using Fourier transform infrared (FTIR) and ¹H nuclear magnetic resonance (NMR) spectroscopic methods, wide‐angle X‐ray diffraction (WAXD), and thermal analysis techniques. WAXD data showed that the obtained ICs with N₃P₃‐(PCL‐Chol)₆ had a channel‐type crystalline structure, indicating the suppression of the original crystallization of N₃P₃‐(PCL‐Chol)₆ in β‐CD cavities. Moreover, the thermal stabilities of ICs were found to be higher than those of the free star polymer and β‐CD. Furthermore, the surface properties of N₃P₃‐(PCL‐Chol)₆ and its ICs with β‐CD were investigated by static contact angle measurements. The obtained results proved that the wettability of N₃P₃‐(PCL‐Chol)₆ successfully increased with the formation of its ICs with β‐CD. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3406–3420     

Mononuclear nickel(II) and zinc(II) complexes with deprotonated forms of the tripodal hexadentate ligand 1,3‐bis(2‐hydroxybenzylidene)‐2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methylpropane‐1,3‐diamine

In the crystal structures of both title compounds, [1,3‐bis(2‐hydroxybenzylidene)‐2‐methyl‐2‐(2‐oxidobenzylideneaminomethyl)propane‐1,3‐diamine]nickel(II) [2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methyl‐1,3‐bis(2‐oxidobenzylidene)propane‐1,3‐diamine]nickel(II) chloride methanol disolvate, [Ni(C₂₆H_25.5N₃O₃)]₂Cl·2CH₄O, and [1,3‐bis(2‐hydroxybenzylidene)‐2‐methyl‐2‐(2‐oxidobenzylideneaminomethyl)propane‐1,3‐diamine]zinc(II) perchlorate [2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methyl‐1,3‐bis(2‐oxidobenzylidene)propane‐1,3‐diamine]zinc(II) methanol trisolvate, [Zn(C₂₆H₂₅N₃O₃)]ClO₄·[Zn(C₂₆H₂₆N₃O₃)]·3CH₄O, the 3d metal ion is in an approximately octahedral environment composed of three facially coordinated imine N atoms and three phenol O atoms. The two mononuclear units are linked by three phenol–phenolate O—H...O hydrogen bonds to form a dimeric structure. In the Ni compound, the asymmetric unit consists of one mononuclear unit, one‐half of a chloride anion and a methanol solvent molecule. In the O—H...O hydrogen bonds, two H atoms are located near the centre of O...O and one H atom is disordered over two positions. The Ni^II compound is thus formulated as [Ni(H_1.5L)]₂Cl·2CH₃OH [H₃L is 1,3‐bis(2‐hydroxybenzylidene)‐2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methylpropane‐1,3‐diamine]. In the analogous Zn^II compound, the asymmetric unit consists of two crystallographically independent mononuclear units, one perchlorate anion and three methanol solvent molecules. The mode of hydrogen bonding connecting the two mononuclear units is slightly different, and the formula can be written as [Zn(H₂L)]ClO₄·[Zn(HL)]·3CH₃OH. In both compounds, each mononuclear unit is chiral with either a Δ or a Λ configuration because of the screw coordination arrangement of the achiral tripodal ligand around the 3d metal ion. In the dimeric structure, molecules with Δ–Δ and Λ–Λ pairs co‐exist in the crystal structure to form a racemic crystal. A notable difference is observed between the M—O(phenol) and M—O(phenolate) bond lengths, the former being longer than the latter. In addition, as the ionic radius of the metal ion decreases, the M—O and M—N bond distances decrease.     

A Novel Dinuclear Nickel(II) Complex with Three Bridges of Cl–, OAc– and (‐OCH2CH2O‐) Group of N,N, N′, N′‐Tetrakis(2‐benzimidazolyl methyl‐1, 4‐di‐ethylene amino) Glycol Ether

The novel dinuclear Ni²⁺ complex [Ni₂(μ‐Cl)(μ‐OAc) (EGTB)]·Cl·ClO₄·2CH₃OH, where EGTB is N, N, N′, N′‐tetrakis (2‐benzimidazolyl methyl‐1, 4‐di‐ethylene amino)glycol ether, crystallizes in the orthorhombic space group Pnma with a = 15.272(2), b = 14.768(2), c = 22.486(3) Å, V = 5071.4(12) ų, Z = 4, D_calc = 1.414 g cm^?3, and is bridged by triply bridging agents of a chloride ion, an acetate and an intra‐ligand (‐OCH₂CH₂O‐) group. The nickel coordination geometry is that of a slightly distorted octahedron with a NiN₃O₂Cl arrangement of the ligand donor atoms. The Ni–Cl distance is 2.361(2) Å, and two Ni–O distances are 1.996(5) and 2.279(6) Å. The three Ni–N distances are 2.033(7), 2.060(6), and 2.166(6) Å with the Ni–N bond trans to an ether oxygen the shortest, the Ni–N bond trans to an acetate oxygen the middle and the Ni–N bond trans to Cl the longest.     

Ethyl 1,4‐dihydro‐4‐oxo‐3‐quinolinecarboxylates by a tandem addition‐elimination‐SNAr reaction

The ethyl 1,4‐dihydro‐4‐oxo‐3‐quinolinecarboxylate ring structure, important in several drug compounds, has been prepared in two steps from ethyl 2‐(2‐fluorobenzoyl)acetate. Treatment of this β‐ketoester with N,N‐dimethylformamide dimethyl acetal gives a 97% yield of the 2‐dimethylaminomethylene derivative. Reaction of this β‐enaminone with primary amines in N,N‐dimethylformamide at 140°C for 48 h then affords the 1,4‐dihydro‐4‐oxo‐3‐quinolinecarboxylate esters in 60–74% yields by a tandem addition‐elimination‐S_NAr reaction. The synthesis of the starting material as well as procedural details and a mechanistic scenario are presented. J. Heterocyclic Chem., (2011).     

Highly Stereoselective β‐Mannopyranosylation via the 1‐α‐Glycosyloxy‐isochromenylium‐4‐gold(I) Intermediates

While the gold(I)‐catalyzed glycosylation reaction with 4,6‐O‐benzylidene tethered mannosyl ortho‐alkynylbenzoates as donors falls squarely into the category of the Crich‐type β‐selective mannosylation when Ph₃PAuOTf is used as the catalyst, in that the mannosyl α‐triflates are invoked, replacement of the ^?OTf in the gold(I) complex with less nucleophilic counter anions (i.e., ^?NTf₂, ^?SbF₆, ^?BF₄, and ^?BAr₄^F) leads to complete loss of β‐selectivity with the mannosyl ortho‐alkynylbenzoate β‐donors. Nevertheless, with the α‐donors, the mannosylation reactions under the catalysis of Ph₃PAuBAr₄^F (BAr₄^F=tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate) are especially highly β‐selective and accommodate a broad scope of substrates; these include glycosylation with mannosyl donors installed with a bulky TBS group at O3, donors bearing 4,6‐di‐O‐benzoyl groups, and acceptors known as sterically unmatched or hindered. For the ortho‐alkynylbenzoate β‐donors, an anomerization and glycosylation sequence can also ensure the highly β‐selective mannosylation. The 1‐α‐mannosyloxy‐isochromenylium‐4‐gold(I) complex ( Cα ), readily generated upon activation of the α‐mannosyl ortho‐alkynylbenzoate ( 1 α ) with Ph₃PAuBAr₄^F at ?35 °C, was well characterized by NMR spectroscopy; the occurrence of this species accounts for the high β‐selectivity in the present mannosylation.