Base-Mediated and Silver-Catalyzed Divergent Synthesis of Hydroxynaphthalenamides and Phosphorylated Dihydronaphthylamides from Enone-Oxazolones.

An efficient divergent approach to functionalized naphthalene derivatives, the naphthalenamides, via base-mediated and silver-catalyzed cyclization has been developed using enone-oxazolones as the precursors. This protocol utilized base in methanol with heating to construct the corresponding hydroxynaphthalenamides 2 by a C-C bond formation, oxazolone ring-opening, and aromatization in good yields. On the other hand, phosphorylated dihydronaphthylamides 3 were generated by using H-phosphonate as the phosphonating reagent in a silver-catalyzed cyclization involving the phospha-1,4-addition/intramolecular ring closure with concomitant C-P/C-C bond formation in good yields.

Woven, Polycatenated, or Cage Structures: Effect of Modulation of Ligand Curvature in Heteroleptic Uranyl Ion Complexes.

Combining the flexible zwitterionic dicarboxylate 4,4'-bis(2-carboxylatoethyl)-4,4'-bipyridinium (L) and the anionic dicarboxylate ligands isophthalate (ipht2-) and 1,2-, 1,3-, or 1,4-phenylenediacetate (1,2-, 1,3-, and 1,4-pda2-), of varying shape and curvature, has allowed isolation of five uranyl ion complexes by synthesis under solvo-hydrothermal conditions. [(UO2)2(L)(ipht)2] (1) and [(UO2)2(L)(1,2-pda)2]·2H2O (2) have the same stoichiometry, and both crystallize as monoperiodic coordination polymers containing two uranyl-(anionic carboxylate) strands united by L linkers into a wide ribbon, all ligands being in the divergent conformation. Complex 3, [(UO2)2(L)(1,3-pda)2]·0.5CH3CN, with the same stoichiometry but ligands in a convergent conformation, is a discrete, binuclear species which is the first example of a heteroleptic uranyl carboxylate coordination cage. With all ligands in a divergent conformation, [(UO2)2(L)(1,4-pda)(1,4-pdaH)2] (4) crystallizes as a sinuous and thread-like monoperiodic polymer; two families of chains run along different directions and are woven into diperiodic layers. Modification of the synthetic conditions leads to [(UO2)4(LH)2(1,4-pda)5]·H2O·2CH3CN (5), a monoperiodic polymer based on tetranuclear (UO2)4(1,4-pda)4 rings; intrachain hydrogen bonding of the terminal LH+ ligands results in diperiodic network formation through parallel polycatenation involving the tetranuclear rings and the LH+ rods. Complexes 1-3 and 5 are emissive, with complex 2 having the highest photoluminescence quantum yield (19%), and their spectra show the maxima positions usual for tris-κ2O,O'-chelated uranyl cations.

Selective electrophilic cyclization of ortho-carbonylarylacetylenols for the synthesis of cyclopenta[a]naphthalenol and 2-phenylnaphthalen-1-ol analogs.

This work demonstrates a new method for the synthesis of cyclopenta[a]naphthalenol and 2-phenylnaphthalen-1-ol analogs via selective cyclization. ortho-Alkynylarylkenones were employed as the common substrates that could be prepared by Sonogashira coupling between 2-haloarylacetophenone and pent-4-yn-1-ol derivatives. These precursors were used without purification to construct 2-phenylnaphthalen-1-ol intermediates by treating with (+)-CSA under heating conditions. Selective cyclization occurred when the reaction was conducted in methyl trimethylacetate solvent which predominantly produced the 2-phenylnaphthalen-1-ol product through 6-endo-dig cyclization without elimination or the formation of cyclopenta[a]naphthalenol via shutting down the 5-exo-dig mode of cyclization. Switching the acid from a Brønsted acid to Bi(OTf)3 led to smooth reactions, providing the cyclopenta[a]naphthalenol products in moderate to good yields. Moreover, we also demonstrated the utilization of 2-phenylnaphthalen-1-ol to prepare naphthoquinone, which is an important core structure of bioactive and natural product compounds.

Simultaneous Occurrence of Vapochromism and Vapoluminescence in Formaldehyde-Responsive Amino-Functionalized Copper(I) Polymorphic Coordination Polymers.

The use of vapor-responsive chromic materials in sensing applications for the detection of harmful volatile organic chemicals is rapidly expanding. Herein, four new amino-functionalized Cu(I) coordination polymers of [CuI(pyt-NH2)]n (1) and (2) and [CuSCN(pyt-NH2)]n (3) and (4) (where pyt-NH2 = 2-amino-5-(4-pyridinyl)-1,3,4-thiadiazole) were successfully synthesized. Single-crystal X-ray diffraction analysis reveals that 1 and 2 are iodo-based polymorphs, while 3 and 4 are thiocyanato-based polymorphs. They possess densely diverse crystalline architectures decorated by uncoordinated amino groups as a binding site. Also, 1-4 show a variety of color and luminescence based on the structural diversity. Remarkably, 1 and 2 undergo the change of color and naked-eye solid-state luminescence in response to formaldehyde (FA) vapor, demonstrating simultaneous vapochromism and vapoluminescence. The chromic Cu(I) coordination polymers in this work present for the first time dual-mode vapochromism and vapoluminescence in a highly selective response to FA vapor. The responsive mechanism has been clarified by Fourier transform infrared spectroscopy (FT-IR), electrospray ionization mass spectrometry (ESI-MS), 1H nuclear magnetic resonance (NMR), powder X-ray diffraction (PXRD), and luminescence lifetime measurements, which reveal carbinolamine formation via the specific reaction between FA and the active amino groups of coordinated pyt-NH2. The carbinolamine formation can trigger the structural transformation of 1 and 2, leading to the concurrently selective vapochromism and vapoluminescence induced by FA vapor.

Incorporation of Cation Affects the Redox Reactivity of Fe-NNN Complexes on C-H Oxidation.

Cations such as Lewis acids have been shown to enhance the catalytic activity of high-valent Fe-oxygen intermediates. Herein, we present a pyridine diamine ethylene glycol macrocycle, which can form Zn(II)- or Fe(III)-complex with the NNN site, while allowing redox-inactive cations to bind to the ethylene glycol moiety. The addition of alkali, alkali earth, and lanthanum ions resulted in positive shifts to the Fe(III/II) redox potential. Calculation of dissociation constants showed the tightest binding with a Ba2+ ion. Density functional theory calculations were used to elucidate the effects of redox inactive cations toward the electronic structures of Fe complexes. Although the Fe-NNN complexes, both in the absence and presence of cations, can catalyze C-H oxidation of 9,10-dihydroanthracene, to give anthracene [hydrogen atom transfer (HAT) product], anthrone, and anthraquinone [oxygen atom transfer (OAT) products], highest overall activity and OAT/HAT product ratios were obtained in the presence of dications, that is, Ba2+ and Mg2+, respectively.

Krabasinolide A with anti-HIVs activity from the leaves and twigs of Croton krabas.

One new clerodane-type diterpenoid, together with one known, was isolated from the leaves and twigs of C. krabas. The structures of these compounds were elucidated as krabasinolide A (1) and taraxerol (2) by spectroscopic methods (UV, IR, HRESIMS, 1 D, and 2 D NMR), and the relative stereochemistry was confirmed by X-ray diffraction analysis with graphite monochromated Mo-Kα (λ = 0.71073 Å) radiation at 296(2) K. Extracts and compounds 1-2 were evaluated for in vitro antiviral activity.

Stem Extract from Momordica cochinchinensis Induces Apoptosis in Chemoresistant Human Prostate Cancer Cells (PC-3).

Natural compounds have been recognized as valuable sources for anticancer drug development. In this work, different parts from Momordica cochinchinensis Spreng were selected to perform cytotoxic screening against human prostate cancer (PC-3) cells. Chromatographic separation and purification were performed for the main constituents of the most effective extract. The content of the fatty acids was determined by Gas Chromatography-Flame Ionization Detector (GC-FID). Chemical structural elucidation was performed by spectroscopic means. For the mechanism of the apoptotic induction of the most effective extract, the characteristics were evaluated by Hoechst 33342 staining, sub-G1 peak analysis, JC-1 staining, and Western blotting. As a result, extracts from different parts of M. cochinchinensis significantly inhibited cancer cell viability. The most effective stem extract induced apoptosis in PC-3 cells by causing nuclear fragmentation, increasing the sub-G1 peak, and changing the mitochondrial membrane potential. Additionally, the stem extract increased the pro-apoptotic (caspase-3 and Noxa) mediators while decreasing the anti-apoptotic (Bcl-xL and Mcl-1) mediators. The main constituents of the stem extract are α-spinasterol and ligballinol, as well as some fatty acids. Our results demonstrated that the stem extract of M. cochinchinensis has cytotoxic and apoptotic effects in PC-3 cells. These results provide basic knowledge for developing antiproliferative agents for prostate cancer in the future.

Highly Regioselective Tandem Reaction of Ene-Yne-Oxazolones Induced by H-Phosphonates: Construction of Phosphinylindane Derivatives.

A highly regioselective divergent approach for the phosphine-containing indane/indene derivatives from the ene-yne-oxazolone precursors was reported. An insight into the reaction mechanism involving the phospha-1,4-addition followed by 5-exo-dig ring closure with a concomitant C-P/C-C bond formation was also proposed. This promising protocol utilized H-phosphonate as the phosphonating reagent in a silver-catalyzed or base-mediated cascade cyclization to construct the corresponding phosphorylated spiroindenoxazolones and amidoindenes, respectively, in good yields (up to 88% yield).

Dibrominative Spirocyclization of 2-Butynolyl Anilides: Synthesis of gem-Dibromospirocyclic Benzo[d][1,3]oxazines and Their Application in the Synthesis of 4H-Furo[3,2-b]indoles.

The combination of catalytic aqueous hydrochloric acid (HCl) and N-bromosuccinimide (NBS) generated electrophilic bromine monochloride (BrCl), which readily induced spiroannulation of 2-alkynolyl anilides (n = 1-3) to form gem-dibromospirocyclic benzo[d][1,3]oxazines in up to 92% yield. The reaction occurred under mild and metal-free conditions using EtOAc as a green solvent. The resulted spirocyclic products contained benzo[d][1,3]oxazine, which was useful both as a pharmacophore and synthetic precursor. In addition, the current protocol allowed to effortlessly introduce the sp3-gem-dibromide carbon adjacent to the sterically demanding spiroketal center. These spiroheterocycles (n = 1) were shown to be synthetically versatile and conveniently maneuvered. Base-promoted debrominative aromatization of these spirocycles unmasked rare and synthetically useful 2-aryl-3-bromofurans in mostly excellent yields. These 3-bromofurans were well-suited substrates for intramolecular Ullmann C-N bond coupling to construct difficult-to-prepare 4H-furo[3,2-b]indoles. Additionally, the current protocol was flexible and adaptable to preparing the gem-dichloride variants.

New ent-kaurane-type diterpenoid with cytotoxic activity from Croton mekongensis.

A new ent-kaurane-type diterpenoid, crotonmekongenin A (1) together with two known compounds, epifriedelanol (2) and sitosterol glucoside (3) from the leaves and twigs of Croton mekongensis were isolated. The structure of these compounds was determined by spectroscopic analysis. The structure of the new ent-kaurane-type diterpenoid (1) was elucidated using spectroscopic technique and X-ray crystallography analysis. Moreover, the cytotoxicity of all extract and isolated compounds was tested for cytotoxicity against KKU-M213, FaDu, HT-29, MDA-MB-231, A-549, SH-SY5Y, and CL cell lines. Compound 1 showed significant cytotoxic activity (ED50) on FaDu (0.48 µg/ml), HT-29 (0.63 µg/ml), and SH-SY5Y (0.45 µg/ml).

Self-Assembly of 1D Double-Chain and 3D Diamondoid Networks of Lanthanide Coordination Polymers through In Situ-Generated Ligands: High-Pressure CO2 Adsorption and Photoluminescence Properties.

Two new lanthanide-based coordination polymers, [Sm2(bzz)(ben)6(H2O)3]·0.5H2O (1) and [Eu(bbz)(ben)3] (2), were synthesized and characterized. The described products were formed from in situ-generated benzoate (ben) and N'-benzoylbenzohydrazide (bbz) ligands, which were the products of transformation of originally added benzhydrazide (bzz) under hydrothermal conditions. Compound 1 exhibits a one-dimensional (1D) double-chain structure built up from the connection of the central Sm3+ ions with a mixture of bzz and ben ligands. On the other hand, 2 features a 3D network with a 4-connected (66) dia topology constructed from dinuclear [Eu2(ben)6] secondary building units and bbz linkers. High-pressure CO2 sorption studies of activated 1 show that maximum uptake increases to exceptionally high values of 376.7 cm3 g-1 (42.5 wt%) under a pressure of 50 bar at 298 K with good recyclability. Meanwhile, 2 shows a typical red emission in the solid state at room temperature with the decay lifetime of 1.2 ms.

Unprecedented Reverse Volume Expansion in Spin-Transition Crystals.

The current craze for research around the spin crossover phenomenon can be justified to some extent by the mechanical properties due to the decrease of volume associated with the transition of the metal ion from the HS state to the LS state. As demonstrated here, the molecular complex [Fe(PM-pBrA)2 (NCS)2 ] exhibits, on the contrary, an increase of the unit-cell volume from HS to LS. This counter-intuitive and unprecedented behavior that concerns both the thermal and the photoexcited spin conversions is revealed by a combination of single-crystal and powder X-ray diffraction complemented by magnetic measurements. Interestingly, this abnormal volume change appears concomitant with the wide rotation of a phenyl ring which induces a drastic modification, though reversible, of the structural packing within the crystal. In addition, the light-induced HS state obtained through the Light-Induced Excited Spin-State Trapping shows a remarkably high relaxation temperature, namely T(LIESST), of 109 K, one of the highest so far reported. The above set of quite unusual characteristics opens up new fields of possibilities within the development of spin crossover materials.

Ring-Opening Copolymerizaton of Cyclohexene Oxide and Succinic Anhydride by Zinc and Magnesium Schiff-Base Complexes Containing Alkoxy Side Arms.

The ring-opening copolymerization (ROCOP) of epoxides and cyclic anhydrides is a promising method for the synthesis of new polyesters with various polymer properties. Among previously reported metal catalysts for ROCOP, the Schiff-base complexes have gained significant attention because of their ease of synthesis and modification. In this work, zinc and magnesium complexes containing Schiff-base ligands with different alkoxy side arms [-(CH2)2O- and -(CH2)3O-] were synthesized and shown to have a cubane metal core by X-ray crystal structures. All complexes were studied in the ROCOP of cyclohexene oxide (CHO) and succinic anhydride (SA) in toluene at 110 °C. The zinc complex having a shorter side arm is the most active catalyst for copolymerization, giving poly(CHO-alt-SA) with narrow dispersity and negligible ether linkage. On the other hand, magnesium complexes were not active because of the formation of stable carboxylate species. The detailed analysis of polyester obtained from zinc complexes unexpectedly revealed three different types of polymer structures occurring at different polymerization times. Cyclic polymer was generated at the beginning by intramolecular transesterification of the alkoxy side arm, giving a low-molecular-weight polyester. At higher conversion, cyclization diminished, giving just a linear polyester but with minor competitive formation of higher-molecular-weight polyester having cyclohexanediol as an end group. On the basis of a thorough understanding of the polymerization mechanism, the desired cyclic poly(CHO-alt-SA) was successfully synthesized using a low monomer/catalyst ratio.

Crystal structure of (pyridin-2-yl-methyl-idene)(tri-phenyl-meth-yl)amine.

The title Schiff base compound, C25H20N2, crystallizes with two independent mol-ecules (A and B) in the asymmetric unit. In both mol-ecules, the imine group is approximately coplanar with the pyridine ring, with N-C-C-N torsion angles of 170.1 (3) and -172.0 (3) Å. In the crystal, A and B dimers are linked by pairs of C-H⋯π inter-actions and further C-H⋯π bonds link the dimers into a three-dimensional network.

Synthesis, crystal structure and properties of poly[di-µ3-chlorido-di-µ2-chlorido-bis-[4-methyl-N-(pyridin-2-yl-methyl-idene)aniline]dicadmium(II)].

The title coordination polymer with the 4-methyl-N-(pyridin-2-yl-methyl-idene)aniline Schiff base ligand (L, C13H12N2), [Cd2Cl4(C13H12N2)] n (1), exhibits a columnar structure extending parallel to [100]. The columns are aligned in parallel and are decorated with chelating L ligands on both sides. They are elongated into a supra-molecular sheet extending parallel to (01) through π-π stacking inter-actions involving L ligands of neighbouring columns. Adjacent sheets are packed into the tri-periodic supra-molecular network through weak C-H⋯Cl hydrogen-bonding inter-actions that involve the phenyl CH groups and chlorido ligands. The thermal stability and photoluminescent properties of (1) have also been examined.

Synthesis, structure and photoluminescence properties of heterometallic-based coordination polymers of trimesic acid.

Reacting trimesic acid (H3TMA, C9H6O6) with CaCl2 and MCl2 at 110 °C under hydrothermal conditions gave the isostructural heterobimetallic coordination polymers (CPs) catena-poly[[tetraaquazinc(II)]-µ-5-carboxybenzene-1,3-dicarboxylato-[tetraaquacalcium(II)]-µ-5-carboxybenzene-1,3-dicarboxylato], [CaZn(HTMA)2(H2O)8]n, 1, and catena-poly[[tetraaquacobalt(II)]-µ-5-carboxybenzene-1,3-dicarboxylato-[tetraaquacalcium(II)]-µ-5-carboxybenzene-1,3-dicarboxylato], [CaCo(HTMA)2(H2O)8]n, 2. Compounds 1 and 2 crystallize in the monoclinic space group C2/c. The solid-state structures consist of eight-coordinate CaII ions and six-coordinate MII ions. These ions are connected by a doubly deprotonated HTMA2- ligand to create a one-dimensional (1D) zigzag chain. Poly[[decaaquabis(µ3-benzene-1,3,5-tricarboxylato)calcium(II)dizinc(II)] dihydrate], {[CaZn2(TMA)2(H2O)10]·2H2O}n, 3, was found incidentally as a minor by-product during the synthesis of 1 at a temperature of 140 °C. It forms crystals in the orthorhombic space group Ccce. The structure of 3 consists of a two-dimensional (2D) layer composed of [Zn(TMA)] chains that are interconnected by CaII ions. The presence of aromatic carboxylic acid ligands and water molecules, which can form numerous hydrogen bonds and π-π interactions, increases the stability of the three-dimensional (3D) supramolecular architecture of these CPs. Compounds 1 and 2 exhibit thermal stability up to 420 °C, as indicated by the thermogravimetric analysis (TGA) curves. The powder X-ray diffraction (PXRD) data reveal the formation of unidentified phases in methanol and dimethyl sulfoxide, while 1 exhibits chemical stability in a wide range of solvents. The luminescence properties of 1 dispersed in various low molecular weight organic solvents was also examined. The results demonstrate excellent selectivity, sensitivity and recyclability for detecting acetone molecules in aqueous media. Additionally, a possible sensing mechanism is also outlined.

Effects of the ligand linkers on stability of mixed-valence Cu(I)Cu(II) and catalytic aerobic alcohol oxidation activity.

We synthesized a class of ligands that feature single (L1) and dual amine-bis(triazole) chelates (L2 with a 1,3-phenylene linker and L3 with a 1,5-naphthalene linker). Our findings which were derived from UV-Vis titrations, crystal structure analysis of relevant copper complexes, and DFT calculations indicate the formation of both mononuclear CuBr(L1) and dinuclear (µ-Ln)(CuBr)2 (Ln = L2 and L3) complexes. The catalytic activities of CuBr/Ln, in combination with TEMPO (2,2,6,6-tetramethylpiperidin-1-yl)oxyl) co-catalyst and NMI (N-methylimidazole) for aerobic alcohol oxidation, reveal the following activity trend: CuBr/L3 > CuBr/L2 > CuBr/L1. Furthermore, electrochemical data from in-situ generated CuBr complexes suggest that the higher catalytic performance of CuBr/L3 is attributed to the presence of less stable mixed-valence and more reducible Cu(I)-L3-Cu(II) species compared to Cu(I)-L2-Cu(II). This difference is a result of weaker σ interactions between Cu-Namine, larger bridging π systems, and a longer Cu···Cu distance in the presence of L3. Additionally, the catalyst system, CuBr/L3/TEMPO/NMI, efficiently promotes the aerobic oxidation of benzyl alcohol to benzaldehyde at room temperature in CH3CN with a high turnover frequency (TOF) of 38 h-1 at 1 h.

Smart and UV-Resistant Edible Coating and Films Based on Alginate, Whey Protein, and Curcumin.

In this work, smart edible coating and films with excellent UV barrier properties were prepared from alginate, whey protein isolate, and curcumin. The primary focus of this investigation centered on assessing the impact of whey protein and curcumin on the physical and functional properties of the alginate films. Whey protein reduced the film transparency while simultaneously enhancing the hydrophobicity and antioxidant properties of the alginate film. Curcumin imparted a yellow hue to the film, consequently decreasing the transparency of the film. It also substantially improved hydrophobicity, antioxidant activity, and UV-blocking efficiency within the films. Remarkably, curcumin demonstrated a significant reduction in the water vapor transmission rate of the film. For the preservation of apples, a higher concentration of curcumin was required, which effectively suppressed the respiration rate and moisture loss post-harvest, resulting in an extended shelf-life for the apples. As a result, the coated apples exhibited significantly reduced enzymatic browning and weight loss in comparison to their uncoated counterparts. Furthermore, these curcumin-containing films underwent a reversible color change from orange to red when exposed to ammonia vapor. This attribute highlights the potential of the developed coating and film as a smart, active food packaging solution, particularly for light-sensitive food products.

Crystal structure and Hirshfeld surface analysis of a new mononuclear copper(II) complex: [bis-(pyridin-2-yl-κN)amine](formato-κO)(m-hy-droxy-benzoato-κ2O,O')copper(II).

A new mononuclear copper(II) complex, [Cu(C7H5O3)(HCO2)(C10H9N3)], containing mixed N- and O-donor ligands, 2,2'-di-pyridyl-amine (dpyam) and m-hy-droxy-benzoate (m-OHbenz), has been obtained from a solvent mixture. The coordination environment of the CuII ion is distorted square-pyramidal with a [N2O3] coordination set originating from the chelating dpyam and m-OHbenz ligands in the basal plane and the O atom of a formato ligand at the apical position. The crystal structure of the title complex is stabilized by N-H⋯O, O-H⋯O, C-H⋯O hydrogen-bonding, π-π and C-H⋯π inter-molecular inter-actions, which were qu-anti-fied by Hirshfeld surface analysis.

Crystal structure of a new europium(III) compound based on thio-phene-acrylic acid.

A europium(III) coordination compound based on thio-phene-acrylic acid (Htpa), tri-aqua-tris-[3-(thio-phen-2-yl)prop-2-enoato-κ2 O,O']europium(III)-3-(thio-phen-2-yl)prop-2-enoic acid (1/3), [Eu(C7H5O2S)3(H2O)3]·3C7H6O2S or [Eu(tpa)3(H2O)3]·3(Htpa) (1), where tpa is the conjugate base of Htpa, has been synthesized and structurally characterized. Compound 1 crystallizes in the trigonal space group R3. The structure of 1 consists of a discrete mol-ecular complex [Eu(tpa)3(H2O)3] species and the Htpa mol-ecule. In the crystal, the two components are involved in O-H⋯O [ring motif R 2 2(8)] and C-H⋯π hydrogen-bonding inter-actions. These inter-actions were further investigated by Hirshfeld surface analysis, which showed high contributions of H⋯H, H⋯C/C⋯H and H⋯O/O⋯H contacts to the total Hirshfeld surfaces.