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High pressure reactivity of phosphorus and hydrogen is relevant to fundamental chemistry, energy conversion and storage, and materials science. Here we report the synthesis of (PH3)2H2, a crystalline van der Waals (vdW) compound (I4cm) made of PH3 and H2 molecules, in a Diamond Anvil Cell by direct catalyst-free high pressure (1.2 GPa) and high temperature (T ≲ 1000 K) chemical reaction of black phosphorus and liquid hydrogen, followed by room T compression above 3.5 GPa. Group 15 elements were previously not known to form H2-containing vdW compounds of their molecular hydrides. The observation of (PH3)2H2, identified by synchrotron X-ray diffraction and vibrational spectroscopy (FTIR, Raman), therefore represents the discovery of a previously missing tile, specifically corresponding to P for pnictogens, in the ability of non-metallic elements to form such compounds. Significant chemical implications encompass reactivity of the elements under extreme conditions, with the observation of the P analogue of the Haber-Bosch reaction for N, fundamental bond theory, and predicted high pressure superconductivity in P-H systems., Chemical elements at high pressure may behave more consistently with their periodic properties than they do at ambient conditions. The authors report the synthesis of PH3 from black phosphorous and hydrogen, and the crystallization of the van der Waals compound (PH3)2H2 which fills a gap in the chemistry of adjacent elements in the periodic table.

Nano-polycrystalline diamonds (NPDs) have become fundamental tools for cutting-edge X-ray absorption spectroscopy (XAS) studies at high P/T conditions that opened up new research directions by over...

The structure and properties of metal-hydrides at extreme conditions is key to the understanding of hydrogen-storage technologies, high-temperature superconductivity, and the dynamics of planetary cores. Here we investigate the phase relations and magnetic properties of iron hydrides, including two novel FeHx compounds, up to 63 GPa and 1800 K by Synchrotron Mössbauer Source spectroscopy and single-crystal X-ray diffraction. We observe the formation of a novel monoclinic iron hydride phase Fe2H∼3 at 63 GPa and 1000 K, which breaks down to a stoichiometric hexagonal closed packed FeH phase upon decompression below 52 GPa at 300 K. The long-range magnetic order in the two newly-synthetized phases persists to higher pressures compared to the well-known double hexagonal closed packed and face-centered cubic phases of FeH. The formation of magnetic Fe-H phases with high hydrogen concentration may influence the magnetic behavior of planetary metallic cores.

We present a new diamond anvil cell design, hereafter called mBX110, that combines both the advantages of a membrane and screws to generate high pressure. It enables studies at large-scale facilities for many synchrotron X-ray techniques and has the possibility to remotely control the pressure with the membrane as well as the use of the screws in the laboratory. It is fully compatible with various gas-loading systems as well as high/low temperature environments in the lab or at large scale facilities. The mBX110 possesses an opening angle of 85° suitable for single-crystal diffraction or Brillouin spectroscopy and a large side opening of 110° which can be used for X-ray inelastic techniques, such as X-ray Raman scattering spectroscopy, but also for X-ray emission, X-ray fluorescence, or X-ray absorption. An even larger opening of 150° can be manufactured enabling X-ray imaging tomography. We report data obtained with the mBX110 on different beamlines with single-crystal diffraction of stishovite up to 55 GPa, X-ray powder diffraction of rutile-GeO2 and tungsten to 25 GPa and 280 GPa, respectively, X-Ray Raman spectra of the Si L-edge in silica to 95 GPa, and Fe Kβ X-ray emission spectra on a basalt glass to 17 GPa.

Solid krypton (Kr) undergoes a pressure-induced martensitic phase transition from a face-centered cubic (fcc) to a hexagonal close-packed (hcp) structure. These two phases coexist in a very wide pressure domain inducing important modifications of the bulk properties of the resulting mixed phase system. Here, we report a detailed in situ x-ray diffraction and absorption study of the influence of the fcc-hcp phase transition on the compression behavior of solid krypton in an extended pressure domain up to 140 GPa. The onset of the hcp-fcc transformation was observed in this study at around 2.7 GPa and the coexistence of these two phases up to 140 GPa, themaximum investigated pressure. The appearance of the hcp phase is also evidenced by the pressure-induced broadening and splitting of the first peak in the XANES spectra. We demonstrate that the transition is driven by a continuous nucleation and intergrowth of nanometric hcp stacking faults that evolve in the fcc phase. These hcp stacking faults are unaffected by high-temperature annealing, suggesting that plastic deformation is not at their origin. The apparent small Gibbs free-energy differences between the two structures that decrease upon compression may explain the nucleation of hcp stacking faults and the large coexistence domain of fcc and hcp krypton. We observe a clear anomaly in the equation of state of the fcc solid at ∼20 GPa when the proportion of the hcp form reaches ∼20%.We demonstrate that this anomaly is related to the difference in stiffness between the fcc and hcp phases and propose two distinct equation of states for the low and high-pressure regimes.

A one-step synthetic procedure for the radical CH alkylation of BODIPY dyes has been developed. This new reaction generates alkyl radicals through the oxidation of boronic acids or potassium trifluoroborates and allows the synthesis of mono-, di-, tri-, and tetraalkylated fluorophores in a good to excellent yield for a broad range of organoboron compounds. Using this protocol, multiple bulky alkyl groups can be introduced onto the BODIPY core thus creating solid-state emissive BODIPY dyes.

A two-step one-pot sequence, involving Ugi reaction followed by base-promoted carbocyclization accompanied by cleavage of the isocyanide-originated amide moiety, has been successfully elaborated in order to provide a fast access to 6,7-dihydro-5H-pyrrolo[3,4-b]pyridin-5-ones. When the cyclizations were run under air atmosphere a subsequent oxidation occurred producing oxidized 7-hydroxy-6,7-dihydro-5H-pyrrolo[3,4-b]pyridin-5-ones.

We report the utilization of a novel catalyst for cycloisomerizations. The novel catalyst system contains gold nanoparticles supported on Al-SBA15, which was prepared by the ball-milling process. We developed a greener methodology for synthesizing spiroindolines under heterogeneous conditions, using this novel class of supported gold nanoparticles in combination with microwave irradiation. The catalyst is highly reusable and selective. Cycloisomerization reaction yields ranged from good to excellent leading to the formation of two novel classes of six- and seven-membered heterocycles, which have been unprecedented so far. The selectivity of the catalyst towards the desired products is high and the reaction can be performed in ethanol as the solvent. A one-pot cascade reaction could be established commencing with the Ugi-reaction to ensure diversity.

A practical three-step protocol for the assembly of triazolobenzodiazepine-fused diketopiperazines and hydantoins has been developed. The synthesis of these tetracyclic ring systems was initiated by an Ugi reaction, which brought together all necessary functionalities for further transformations. The Ugi adducts were then subjected to a base-induced ring closing and an intramolecular azide–alkyne cycloaddition reaction in succession to obtain highly fused benzodiazepine frameworks.

Evolution can increase the complexity of matter by self-organization into helical architectures, the best example being the DNA double helix. One common aspect, apparently shared by most of these architectures, is the presence of covalent bonds within the helix backbone. Here, we report the unprecedented crystal structures of a metal complex that self-organizes into a continuous double helical structure, assembled by non-covalent building blocks. Built up solely by weak stacking interactions, this alternating tread stairs-like double helical assembly mimics the DNA double helix structure. Starting from a racemic mixture in aqueous solution, the ruthenium(II) polypyridyl complex forms two polymorphic structures of a left-handed double helical assembly of only the Λ-enantiomer. The stacking of the helices is different in both polymorphs: a crossed woodpile structure versus a parallel columnar stacking. ispartof: Angewandte Chemie - International Edition vol:53 issue:34 pages:8959-8962 ispartof: location:Germany status: published

A prototype of a high-pressure cooling apparatus dedicated to macromolecular crystallography on synchrotrons is reported. The system allows cooling of biological crystals without the addition of penetrating or nonpenetrating exogenous cryoprotectant by transforming the aqueous solvent into high-density amorphous ice at a pressure of 200 MPa. The samples are directly fished from crystallization trays with cryopins specifically designed for the pressurizing device and which are compatible with robotized sample changers on synchrotron beamlines. Optionally, the system allows noble gas derivatization during the high-pressure cooling procedure. Some technical details of the equipment and of the method are described in this article. A representative series of test crystals shows that the system is capable of successfully cooling samples that normally require a wide variety of cryoprotection conditions. The last section focuses on pressure-induced structural modifications of these proteins, which are shown to be few but nevertheless of interest.

Recent advancements in radio-frequency resonator designs have led to the implementation of nuclear magnetic resonance in diamond anvil cells (DACs) at pressures well above 100 GPa. However, a relatively low resolution and the absence of decoupling sequences complicate the analysis of the results of solid state NMR in DACs. Here, we present the first application of homo-nuclear Lee-Goldburg (LG) decoupling at extreme conditions on high density molecular hydrogen. Lenz lens based two-dimensional resonator structures were found to generate a homogeneous B1 field across sample cavities as small as 12 picolitres, a prerequisite for optimal decoupling. At ideal LG conditions, the broad 1H resonance of molecular ortho-hydrogen was narrowed 1600-fold, resulting in line-widths of 3.1 ppm.

The UV-vis electronic absorption and fluorescence emission properties of 8-halogenated (Cl, Br, I) difluoroboron dipyrrin (or 8-haloBODIPY) dyes and their 8-(C, N, O, S) substituted analogues are reported. The nature of the meso-substituent has a significant influence on the spectral band positions, the fluorescence quantum yields, and lifetimes. As a function of the solvent, the spectral maxima of all the investigated dyes are located within a limited wavelength range. The spectra of 8-haloBODIPYs display the narrow absorption and fluorescence emission bands and the generally quite small Stokes shifts characteristic of classic difluoroboron dipyrrins. Conversely, fluorophores with 8-phenylamino (7), 8-benzylamino (8), 8-methoxy (9), and 8-phenoxy (10) groups emit in the blue range of the visible spectrum and generally have larger Stokes shifts than common BODIPYs, whereas 8-(2-phenylethynyl)BODIPY (6) has red-shifted spectra compared to ordinary BODIPY dyes. Fluorescence lifetimes for 6, 8, and 10 have been measured for a large set of solvents and the solvent effect on their absorption and emission maxima has been analyzed using the generalized Catalán solvent scales. Restricted rotation about the C8-N bond in 7 and 8 has been observed via temperature dependent (1)H NMR spectroscopy, whereas for 10 the rotation about the C8-O bond is not hindered. The crystal structure of 8 demonstrates that the short C8-N bond has a significant double character and that this N atom exhibits a trigonal planar geometry. The crystal structure of 10 shows a short C8-O bond and an intramolecular C-H···π interaction. Quantum-chemical calculations have been performed to assess the effect of the meso-substituent on the spectroscopic properties.

The ionic liquid choline bis(trifluoromethylsulfonyl)imide, [Chol][Tf2N], was used for the extraction of neodymium(III), in combination with choline hexafluoroacetylacetonate, [Chol][hfac], as the extractant. The binary mixture of [Chol][Tf2N] and water shows temperature-dependent phase behavior, with an upper critical solution temperature of 72 °C. A novel extraction technique, homogeneous liquid–liquid extraction (HLLE), was applied to this solvent system. HLLE is based on the use of thermomorphic solvent mixtures and has the advantage of forming a homogeneous phase during mixing. Extraction is not kinetically hindered by an interface and the extraction equilibrium is reached faster than in the case of heterogeneous mixing in conventional solvent extraction. Several extraction parameters were studied for the extraction of neodymium(III) with [Chol][hfac]: temperature, pH, extractant concentration and loading of the ionic liquid phase. A speciation study was performed to determine the stoichiometry of the extracted neodymium(III) complex and a plausible extraction mechanism is proposed. Neodymium is extracted as a tetrakis hexafluoroacetylacetonate complex with one choline cation as counter ion. The crystal structure of the extracted complex showed the presence of a coordination bond between the choline counter ion and the neodymium(III) center, resulting in a coordination number of nine. The stripping of the loaded neodymium and the influence of acid and extractant concentrations on the phase behavior of the [Chol][Tf2N]–H2O system were investigated. crosscheck: This document is CrossCheck deposited related_data: Crystal Structure Data copyright_licence: The Royal Society of Chemistry has an exclusive publication licence for this journal copyright_licence: The accepted version of this article will be made freely available in the Chemical Sciences Article Repository after a 12 month embargo period history: Received 5 May 2014; Accepted 7 June 2014; Advance Article published 18 June 2014; Version of Record published 8 July 2014 ispartof: Dalton Transactions vol:43 issue:30 pages:11566-11578 ispartof: location:England status: published

Imino-quinolyl ligands L1–L5 were synthesized by condensation reactions and obtained in good yields. Reactions of the ligands with either PdCl2(cod) or K2[PtCl4] gave the corresponding palladium(II) and platinum(II) complexes 1–10 also in good yields. All the compounds were characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy. X-ray crystallography was used to confirm the structures of these compounds. Molecular structures of 3 and 5 showed that the ligands coordinate to the metal center through the two nitrogen atoms, generating a distorted square planar geometry around the palladium atom. The new complexes exhibited remarkable cytotoxic activities against MCF-7 and HT-29 cancer cell lines.

The presence of carbonates in inclusions in diamonds coming from depths exceeding 670 km are obvious evidence that carbonates exist in the Earth’s lower mantle. However, their range of stability, crystal structures and the thermodynamic conditions of the decarbonation processes remain poorly constrained. Here we investigate the behaviour of pure iron carbonate at pressures over 100 GPa and temperatures over 2,500 K using single-crystal X-ray diffraction and Mössbauer spectroscopy in laser-heated diamond anvil cells. On heating to temperatures of the Earth’s geotherm at pressures to ∼50 GPa FeCO3 partially dissociates to form various iron oxides. At higher pressures FeCO3 forms two new structures—tetrairon(III) orthocarbonate Fe43+C3O12, and diiron(II) diiron(III) tetracarbonate Fe22+Fe23+C4O13, both phases containing CO4 tetrahedra. Fe4C4O13 is stable at conditions along the entire geotherm to depths of at least 2,500 km, thus demonstrating that self-oxidation-reduction reactions can preserve carbonates in the Earth’s lower mantle., Carbonates are shown to exist in the lower mantle as seen in diamond inclusions, but thermodynamic constraints are poorly understood. Here, the authors synthesise two new iron carbonate compounds and find that self-oxidation-reduction reactions can preserve carbonates in the mantle.

A method to separate the non-resonant inelastic X-ray scattering signal of a micro-metric sample contained inside a diamond anvil cell (DAC) from the signal originating from the high-pressure sample environment is described. Especially for high-pressure experiments, the parasitic signal originating from the diamond anvils, the gasket and/or the pressure medium can easily obscure the sample signal or even render the experiment impossible. Another severe complication for high-pressure non-resonant inelastic X-ray measurements, such as X-ray Raman scattering spectroscopy, can be the proximity of the desired sample edge energy to an absorption edge energy of elements constituting the DAC. It is shown that recording the scattered signal in a spatially resolved manner allows these problems to be overcome by separating the sample signal from the spurious scattering of the DAC without constraints on the solid angle of detection. Furthermore, simple machine learning algorithms facilitate finding the corresponding detector pixels that record the sample signal. The outlined experimental technique and data analysis approach are demonstrated by presenting spectra of the SiL2,3-edge and OK-edge of compressed α-quartz. The spectra are of unprecedented quality and both the OK-edge and the SiL2,3-edge clearly show the existence of a pressure-induced phase transition between 10 and 24 GPa.

A comparative study on transition metal-catalyzed cycloisomerizations of propargylic ureas derived in situ from secondary propargylic amines and tosyl isocyanate was performed. The influence of catalytic system on the reaction outcome was thoroughly studied on two model examples resulting in the establishment of two selective protocols for both O- and N-cyclizations. The application of cationic gold(I) catalysis generally resulted in a formation of oxazolidin-2-imines as major products while the application of silver(I) triflate selectively provided the corresponding imidazolidin-2-ones. An attempt to rationalize the observed chemoselectivity is described. The scope of both processes was demonstrated through the use of variously substituted secondary propargylic amines.

The title compounds are prepared by domino cyclization of Ugi-adducts using XantPhos or BINAP as ligand.

International audience; We have developed an experimental setup at the ESRF beamline ID12 dedicated to X-ray absorption and magnetic circular dichroism measurements at high pressure adapted for the tender X-ray energy range and compatible with low temperatures and with high magnetic field. The focused incoming X-ray beam passes through a thin diamond disk attached to a fully perforated diamond anvil and X-ray fluorescence photons from the sample are collected in back-scattering geometry through the same diamond disk. The pressure in the cell is measured using the ruby luminescence through a full diamond anvil. The highest pressure attainable with this diamond anvil cell (DAC) depends on the thickness of the diamond disk and it is above 16 GPa for a 80-μm thick plate and exceeds 4.5 GPa in the case of 30-μm diamond disk. Excellent performances of this setup in the tender X-ray range are illustrated with X-ray absorption near-edge structure studies of the phase transitions in KCl at the potassium and chlorine K-edges (3.61 and 2.82 keV, respectively) as well as in CdS at the sulfur K-edge (2.47 keV). This DAC together with a dedicated total fluorescence yield (TFY) detector could be mounted in the main heat exchanger of a cryostat and inserted in a bore of a superconducting magnet, this makes possible to perform X-ray magnetic circular dichroism (XMCD) experiments at low temperature, high magnetic field and high pressure. Feasibility of this approach is shown with the XMCD results obtained at the U M4,5-edges in ferromagnetic superconductor UGe2.

A novel diversity-oriented access to (spiro)polyheterocycles possessing two adjacent quaternary carbon stereocenters is described. By combining an Ugi 4-CR with Pd-catalysis, the possible mode of cyclization is controlled by the appropriate choice of ligands. Using XantPhos, spirooxindoles are selectively generated, while with BINAP fused polycyclic cis-dihydrobenzofurans are obtained with high diastereoselectivity.

Recently, the diterpenoids steviol and isosteviol, respectively the aglycone and its rearrangement product of the steviol glycosides, have gained a growing interest. Their biological properties have encouraged many scientists to synthesize a considerable amount of analogues. In this Letter, we present three novel (iso)steviol derivatives in which the complex ring structures of the ent- kaurene steviol and ent- beyerane isosteviol are expanded via two highly stereoselective reaction pathways. For steviol, we expanded the structure by carbonyl ene reaction, followed by either formation of a lactone or a pyrane-3(2 H )-one in good yields. Isosteviol was converted into a diene, followed by Diels–Alder reaction.

Gold-catalyzed carbocyclization and heteroannulation strategies have recently attracted much attention owing to the selective and efficient activation of the C C bond towards a wide range of nucleophiles that these methods provide. Domino approaches involving gold-catalysis lead to complex heterocyclic compounds under exceedingly mild reaction conditions. Although gold-catalyzed approaches are rising to prominence, they suffer in terms of diversity and procedural length. Multistep sequences are usually required for assembling the starting material for cyclization. We have recently reported a concise route to indoloazocines by a sequential Ugi/gold-catalyzed intramolecular hydroarylation approach. Inspired by these findings and as a result of our continued synthetic interest in the indole core, multicomponent reactions and transition metal-catalysis, we have developed a post-Ugi gold-catalyzed domino cyclization method to generate spiroindolines. The Ugi four-component reaction (4-CR) of indole-3carboxaldehyde (1a) with p-methoxybenzyl amine (2a), 2-butynoic acid (3a) and tert-butyl isonitrile (4a) in methanol at 50 8C gave Ugi-adduct 5a in 71% yield. When this was treated with 5 mol% of Au[PPh3]OTf (OTf= trifluoromethanesulfonate) in CDCl3 at RT, the expected outcome of the reaction was indoloazepinone 6a’ through an endo-dig cyclization followed by rearrangement (Scheme 1). Surprisingly, an exo-dig cyclization followed by intramolecular trapping of the spiro intermediate occurred instead, resulting in the diastereoselective formation of tetracyclic spiroindoline 6a in 61% yield (Scheme 1). This observation was remarkable, as the attack on the a-position of an alkyne conjugated with an amide is rare, and trapping of the spiro intermediate by a sterically hindered tert-butyl amide is rather unexpected, as was the diastereoselectivity observed. Spiroindolines are prominent molecular motifs that are frequently encountered among the large family of alkaloids; for example, it is present in communesines and perophoramidines (Figure 1), which display distinct pharmacological properties. These fused polycyclic systems, which feature quaternary stereocenters, present a nontrivial challenge for organic chemists to develop synthetic approaches.

A new pneumatic diamond anvil cell has been constructed, generating continuous pressure and temperature variations in the range 0–2.5 GPa and 293–393 K. The cell is designed mainly for high-pressure macromolecular crystallography and should facilitate pressure and temperature annealing of the sample. The analysis is reported of several diffraction data sets of tetragonal hen egg-white lysozyme crystals loaded either in the new cell or in a currently used membrane-based cell. These experiments were performed on beamline FIP-BM30A at the ESRF, Grenoble, a macromolecular crystallography beamline on a bending magnet. Cells were handled and automatically centred by a six-axis robotic arm that was used as a goniometer for data collection by the oscillation method.

The stability domains and equations of state of α-Fe, ϵ-Fe, and γ-Fe have been measured using X-ray diffraction under conditions close to their triple point: 7 ≤ P ≤ 20 GPa and 480 ≤ T ≤ 820 K. Special attention was paid to ensure the hydrostatic compression of the sample, which was a single crystal at start. Narrow α − γ and α − ϵ coexistence domains were observed, while the γ − ϵ transformation appeared sluggish. The triple point is measured at 8.7 ± 1.0 GPa and 750 ± 30 K. Anharmonic effects are evidenced in the equation of state of ϵ-Fe and partly reproduced using ab initio molecular dynamics simulations.

© 2016 ARKAT-USA Inc. A series of novel 3-azolylpyrazolo[5,1-c][1,2,4]triazines was synthesized by reaction of 3-substituted pyrazole-5-diazonium salts with β-azolyl enamines in an efficient fashion. The structures of the compounds prepared were characterized by NMR spectroscopy, massspectrometry, elemental and X-ray diffraction analyses. Plausible mechanisms were formulated. ispartof: Arkivoc vol:2016 issue:4 pages:114-129 status: published

The diamond anvil cell (DAC) is a fundamental device used to explore the properties of materials under extreme pressure and temperature (P/T) conditions. In the past years, simultaneous high P/T DAC experiments using the resistively heated DAC (RH-DAC) techniques have been developed for studying materials properties in a wide P/T range. However, the mechanical instability of metallic gaskets used for sample confinement at high P/T conditions remains a limiting factor for exploiting the accessible P/T range of the RH-DAC. In this study, we present a new gasket configuration that overcomes these limitations. It is based on an amorphous boron–epoxy mixture inserted in a rhenium gasket. We show how these gasket inserts stabilize the sample chamber over a wide P/T range, allowing monitoring sample properties using X-ray diffraction and absorption spectroscopy up to 50 GPa and 1620 K.

A one-pot sequential A3-coupling-azidation-cyclisation approach leading to potentially biologically active diazepine analogues has been developed. The implementation of the A3-coupling reaction ensures diversity. Attention is given to this so far rarely studied structural motif of fused heterocyclic diazepines.

A new azide functionalized Anderson polyoxometalate was synthesized, fully characterized and subsequently used as a building block for further POM post-functionalization with organic compounds through a copper catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Optimization of the reaction conditions led to an efficient, fast, convenient and versatile POM coupling method. crosscheck: This document is CrossCheck deposited related_data: Supplementary Information related_data: Crystal Structure Data copyright_licence: The Royal Society of Chemistry has an exclusive publication licence for this journal history: Received 11 September 2015; Accepted 7 October 2015; Advance Article published 21 October 2015; Version of Record published 3 November 2015 ispartof: Dalton Transactions vol:44 issue:44 pages:19059-19062 ispartof: location:England status: published

The novel catalyst system contains gold nanoparticles supported on Al-SBA15 prepared by the ball-milling process.

A two step one-pot sequence involving Ugi reaction followed by base promoted carbocyclization allows the synthesis of pyrrolopyridine (IV).

In the present study, we have investigated different strategies for diastereoselective synthesis of thia[n]helicenes. We describe the introduction of different chiral auxiliaries at various positions and investigated their effect in the photocyclization reaction. Different chiral groups were placed at the sterically hindered position of the helical core and their interactions with various solvents and metals like copper were investigated. The use of Cu(I) salts has led to high diastereoselectivity in the photocyclization process and we were successful in obtaining the thia[5]helicene in enantiomerically pure form in good yield. The single diastereomer obtained was characterized by X-ray crystallography. From the study of the barrier of racemization of these thia[5]helicenes, the stability was found to be comparable to unsubstituted tetrathia[7]helicenes and substituted diazadithia[7]helicenes. This approach provides an easy access to enantiopure helicenes.

The title imino–phosphine compound, [PdCl2(C26H22NP)]·CH3CN, was prepared by reaction ofN-[2-(diphenylphosphanyl)benzylidene]-2-methylaniline with dichlorido(cycloocta-1,5-diene)palladium(II) in dry CH2Cl2. The PdIIcation is coordinated by the P and N atoms of the bidentate chelating ligand and by two chloride anions, generating a distorted square-planar coordination geometry. There is a detectabletransinfluence for the chloride ligands. The methyl group present in this structure has an influence on the crystal packing.

Microstructures govern the mechanical properties of materials and change dramatically during phase transformations. A detailed understanding of microstructures at different stages of a transformation is important for the design of new materials and for constraining geophysical processes. However, experimental studies of transformation microstructures at the grain scale have been mostly based onex situobservations of quenched products, which are difficult to correlate with bulk sample properties and transformation kinetics. Here, it is shown how multi-grain crystallography on polycrystalline samples, combined with a resistively heated diamond anvil cell, can be applied to investigate the microstructural properties of a material undergoing a phase transitionin situat high pressure and high temperature. This approach allows the extraction of the crystallographic parameters and orientations of several hundreds of grains inside a transforming sample. Important bulk information on grain size distributions and orientation relations between the parent and the newly formed phase at the different stages of the transformation can be monitored. These data can be used to elucidate transformation mechanisms (e.g.coherentversusincoherent growth), growth rates and orientation-dependent growth of individual grains. The methodology is demonstrated on the α–γ phase transitions in hydrous Mg2SiO4·H2O up to 22 GPa and 940 K. This transformation most likely occurs in the most abundant mineral of the Earth's upper mantle (Mg0.8Fe0.2SiO4) in deep cold subducted slabs and plays an important role in their subduction behaviour.

The tuning of selective ring closure is a nontrivial challenge in synthetic organic chemistry. Herein we report a solvent switchable metal-free [4 + 2] cycloaddition approach via Csp(2)-H functionalization. The protocol is highly atom economical with water being the only by-product, delivering N-substituted benzo[e]- or [f]isoindolones in high yields.

Cationic gold-catalyzed cycloisomerizations of propargylureas, derived in situ from secondary propargylamines and aryl or alkyl isocyanates, have been studied. The reaction outcome was found to be different from what was previously observed for the tosyl isocyanate-derived ureas in terms of both regio- and chemoselectivity. As a result, the current protocol offers efficient access to the 3,4-dihydropyrimidin-2(1H)-one core through the 6-endo-dig N-cyclization.

Cationic gold-catalyzed cycloisomerizations of propargylureas, derived in situ from secondary propargylamines and aryl or alkyl isocyanates, have been studied. The reaction outcome was found to be different from what was previously observed for the tosyl isocyanate-derived ureas in terms of both regio- and chemoselectivity. As a result, the current protocol offers efficient access to the 3,4-dihydropyrimidin-2(1H)-one core through the 6-endo-dig N-cyclization.

The reduction of cyclic bistetrasulfide (II) and a subsequent oxidation of intermediate thiolate with air gives rise to cyclic compound (III) bearing disulfide bridges.

Application of cationic Au(I) catalysis generally results in the formation of oxazolidin product (III) as a major one while the application of AgOTf selectively provides the N-cyclized imidazolidin (IV).

A gold-catalyzed regioselective tandem cyclization of N-propynylbutynamide via Csp(3)-H functionalization has been described, providing a distinctive methodology for the architecture of cyclopentapyridinones as well as spirocyclopentapyridinones.

Disulfide bridged pillararene-like macrocycles were synthesized starting from 1,4-dialkoxybenzene and sulfur monochloride. The structure was determined using X-ray diffraction analysis.