An unexpected Pummerer rearrangement in the synthetic route to ethyl (2′-hydroxy-4′,5′-methylenedioxyphenyl)acetate: An alternative approach to 2,3-dimethylthio benzofurans

The synthesis of ethyl (2′-hydroxy-4′,5′-methylendioxophenyl)acetate, a fragment of the antihyperglycemic natural coumarin subcoriacin, is reported. We found an expeditious route to the title compound in five steps. Final metal catalyzed acid ethanolysis of the vinylic 1,1-methylthio methylsulfoxide derivative afforded the required aryl acetic ester, but in the absence of metal catalyst, an unexpected Pummerer rearrangement produced the 2,3-dimethylthiofuran derivative as the major product. This last result provides an alternative entry to 2,3-dimethlythiobenzofurans.     

Green solvent approach for printable large deformation thermoplastic elastomer based piezoresistive sensors and their suitability for biomedical applications

Composites based on biocompatible thermoplastic elastomer styrene‐ethylene/butylene‐styrene (SEBS) as matrix and multi‐walled carbon nanotubes (MWCNT) as nanofillers show excellent mechanical and piezoresistive properties from low to large deformations. The MWCNT/SEBS composites have been prepared following a green solvent approach, to extend their range of applicability to biomedical applications. The obtained composites with 2, 4, and 5 wt % MWCNT content provide suitable piezoresistive response up to 80% deformation with a piezoresistive sensibility near 2.7, depending on the applied strain and MWCNT content. Composite sensors were also developed by spray and screen printing and integrated with an electronic data acquisition system with RF communication. The possibility to accurately control the composites properties and performance by varying MWCNT content, viscosity, and mechanical properties of the polymer matrix, shows the large potential of the system for the development of large deformation printable piezoresistive sensors. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2092–2103     

Montecrinanes A–C: Triterpenes with an Unprecedented Rearranged Tetracyclic Skeleton from Celastrus vulcanicola. Insights into Triterpenoid Biosynthesis Based on DFT Calculations

Three new triterpenoids with an unprecedented 6/6/6/6‐fused tetracyclic carbon skeleton, montecrinanes A–C ( 1 – 3 ), were isolated from the root bark of Celastrus vulcanicola, along with known D:B‐friedobaccharanes ( 4 – 6 ), and lupane‐type triterpenes ( 7 – 12 ). The stereostructures of the new metabolites were elucidated based on spectroscopic (1D and 2D NMR) and spectrometric (HR‐EIMS and HR‐ESIMS) techniques. Their absolute configurations were determined by both NMR spectroscopy, with (R)‐(?)‐α‐methoxyphenylacetic acid as a chiral derivatizing agent, and biogenetic considerations. Biogenetic pathways for montecrinane and D:B‐friedobaccharane skeletons were proposed and studied by DFT methods. The theoretical results support the energetic feasibility of the putative biogenetic pathways, in which the 1,2‐methyl shift from the secondary baccharenyl cation represents a novel and key reaction step for a new montecrinane skeleton.     

pH-Dependent Hydration Change in a Gd-Based MRI Contrast Agent with a Phosphonated Ligand

The heptadentate ligand L was shown to form an extremely stable Gd complex at neutral pH with a pGd value of 18.4 at pH 7.4. The X-ray crystal structures of the complexes formed with Gd and Tb displayed two very different coordination behaviors being, respectively, octa- and nonacoordinated. The relaxometric properties of the Gd complex were studied by field-dependent relaxivity measurements at various temperatures and by ¹⁷O NMR spectroscopy. The pH-dependence of the longitudinal relaxivity profile indicated large changes around neutral pH leading to a very large value of 10.1 mm ⁻¹⋅s⁻¹ (60 MHz, 298 K) at pH 4.7. The changes were attributed to an increase of the hydration number from one water molecule in basic conditions to two at acidic pH. A similar trend was observed for the luminescence of the Eu complex, confirming the change in hydration state. DOSY experiments were performed on the Lu analogue, pointing to the absence of dimers in solution in the considered pH range. A breathing mode of the complex was postulated, which was further supported by ¹H and ³¹P NMR spectroscopy of the Yb complex at varying pH and was finally modeled by DFT calculations.     

Metallacarboranes as Photoredox Catalysts in Water

Metallacarboranes with the shape of the Greek letter θ, such as [Co(C₂B₉H₁₁)₂]⁻, were tested, for the first time, as efficient photoredox catalysts in the oxidation of aromatic and aliphatic alcohols in water. Their efficiency is linked to their high solubility in water, their high oxidizing power (Co^4+/3+), and their absence of fluorescence on excitation, among others. In most of the studied examples, using a catalyst load of 0.4 mol % gave high yields of 90–95 % with selectivity greater than 99 %. By reducing the catalyst load to 0.01 mol %, quantitative conversion of reactants to products was achieved, in some cases with greater than 99 % yield, high catalyst efficiency reaching a turnover number of 10 000, and a higher yield with a 45 times lower concentration of catalyst. The metallacarboranes can be recovered easily by precipitation on addition of [NMe₄]Cl. A pathway for the photoredox-catalyzed oxidation of alcohols is proposed.     

High-Spin and Reactive Fe13 Cluster with Exposed Metal Sites

Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp*₄W₄Fe₁₃S₁₂ , displaying a Fe₁₃ core with M−M bonds that has precedent only in main group and late metal chemistry. M₁₃ clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp*₄W₄Fe₁₃S₁₂ displays a large spin ground state of S=13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.     

A Mononuclear Uranium(IV) Single‐Molecule Magnet with an Azobenzene Radical Ligand

A tetravalent uranium compound with a radical azobenzene ligand, namely, [{(SiMe₂NPh)₃‐tacn}U^IV(η²‐N₂Ph₂^.)] ( 2 ), was obtained by one‐electron reduction of azobenzene by the trivalent uranium compound [U^III{(SiMe₂NPh)₃‐tacn}] ( 1 ). Compound 2 was characterized by single‐crystal X‐ray diffraction and ¹H NMR, IR, and UV/Vis/NIR spectroscopy. The magnetic properties of 2 and precursor 1 were studied by static magnetization and ac susceptibility measurements, which for the former revealed single‐molecule magnet behaviour for the first time in a mononuclear U^IV compound, whereas trivalent uranium compound 1 does not exhibit slow relaxation of the magnetization at low temperatures. A first approximation to the magnetic behaviour of these compounds was attempted by combining an effective electrostatic model with a phenomenological approach using the full single‐ion Hamiltonian.     

High Sensitive Microsensor Based on Organic‐Inorganic Composite for Two‐Dimensional Mapping of H2O2 by SECM

The present work describes the development of a selective, sensitive and stable sensing microsensor for scanning electrochemical microscopy (SECM) to measure H₂O₂ during electrochemical reduction of oxygen. The microsensor is based on graphene and Poly(3,4‐ethylenedioxythiophene) composite as support to iron (III) hexacyanoferrate (II) (PEDOT/graphene/Fe^III₄[Fe^II(CN)₆]₃ microsensor). The electrochemical properties of the PEDOT/graphene/Fe^III₄[Fe^II(CN)₆]₃ microsensor were investigated by cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM). The PEDOT/graphene/Fe^III₄[Fe^II(CN)₆]₃ microsensor showed an excellent electrocatalytic activity toward hydrogen peroxide (H₂O₂) reduction with a diminution of the overpotential of about 500 mV in comparison to the process at a bare gold microelectrode. The microsensor presented excellent performance for two dimensional mapping of H₂O₂ by SECM in 0.1 mol L^?1 phosphate buffer solution (pH 7.0). Under optimized conditions, a linear response range from 1 up to 1000 µmol L^?1 was obtained with a sensitivity of 0.08 nA L µmol^?1 and limit of detection of 0.5 µmol L^?1.