A Structurally Robust Chiral Borate Ion: Molecular Design,Synthesis, and Asymmetric Catalysis

Catalysis by chiral weakly‐coordinating anions (WCAs) remains underdeveloped due to the lack of a molecular design strategy for exploiting their characteristics, such as the non‐nucleophilic nature. Here, we report the development of a chiral borate ion comprising an O,N,N,O‐tetradentate backbone, which ensures hitherto unattainable structural robustness. Upon pairing with a proton, the hydrogen borate acts as an effective catalyst for the asymmetric Prins‐type cyclization of vinyl ethers, providing access to structurally and stereochemically defined dihydropyrans. The key to selectivity control is the distinct ability of the borate ion to discriminate the prochiral faces of the acyclic oxonium ion intermediate and dictate the regiochemical outcome. We anticipate that this study paves the way for exploring the untapped potential of WCA catalysis for selective chemical synthesis.     

Shimalactone Biosynthesis Involves Spontaneous Double Bicyclo-Ring Formation with 8π-6π Electrocyclization

Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo-ring formation reactions proceed non-enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo-ring formation and 8π-6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non-enzymatic conversion to shimalactones in the dark.     

Core–Shell‐Structured LaTaON2 Transformed from LaKNaTaO5 Plates for Enhanced Photocatalytic H2 Evolution

LaTaON₂ is a photocatalyst with intense visible light absorption up to 650 nm, but exhibits low H₂ evolution activity owing to uncontrolled facets and high defect densities. In this work, core–shell‐structured plate‐like LaKNaTaO₅/LaTaON₂ was synthesized by nitriding a layered perovskite‐type LaKNaTaO₅. The volatilization of K and Na species during the nitridation promoted the rapid transformation of LaKNaTaO₅ into LaTaON₂ along [010] direction with the plate‐like shape retained. This yielded high‐quality LaTaON₂ shells exposing (010) facets on the lattice‐matched LaKNaTaO₅ cores. After loading with a Rh co‐catalyst, LaKNaTaO₅/LaTaON₂ showed photocatalytic H₂ evolution activity four times greater than that obtained from conventional irregular‐shaped LaTaON₂ powders and utilized visible light up to 620 nm. This work provides a novel strategy yielding oxynitrides with well‐defined facets and low defect densities by selecting lattice‐matched oxide precursors containing volatile components.     

π–π Stacking Interaction in an Oxidized CuII–Salen Complex with a Side-Chain Indole Ring: An Approach to the Function of the Tryptophan in the Active Site of Galactose Oxidase

In order to gain new insights into the effect of the π–π stacking interaction of the indole ring with the Cu^II–phenoxyl radical as seen in the active form of galactose oxidase, we have prepared a Cu^II complex of a methoxy-substituted salen-type ligand, containing a pendent indole ring on the dinitrogen chelate backbone, and characterized its one-electron-oxidized forms. The X-ray crystal structures of the oxidized Cu^II complex exhibited the π–π stacking interaction of the indole ring mainly with one of the two phenolate moieties. The phenolate moiety in close contact with the indole moiety showed the characteristic phenoxyl radical structural features, indicating that the indole ring favors the π–π stacking interaction with the phenoxyl radical. The UV/Vis/NIR spectra of the oxidized Cu^II complex with the pendent indole ring was significantly different from those of the complex without the side-chain indole ring, and the absorption and CD spectra exhibited a solvent dependence, which is in line with the phenoxyl radical–indole stacking interaction in solution. The other physicochemical results and theoretical calculations strongly support that the indole ring, as an electron donor, stabilizes the phenoxyl radical by the π–π stacking interaction.     

Cyanide-Free One-Pot Synthesis of Methacrylic Esters from Acetone

Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF₃CH₂, and n-C₆F₁₃CH₂CH₂ esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C₆F₁₃CH₂CH₂ esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d₆ and MeOH-d₄, with DBU in acetonitrile afforded deuterated MMA (MMA-d₈) in 70 % yield.     

Photoinduced Pyramidal Inversion Behavior of Phosphanes Involved with Aggregation-Induced Emission Behavior

Aggregation-induced emission (AIE) is a fascinating phenomenon because of the applications of luminescent materials in the aggregated state, which exploit the large structural changes of the molecules in the excited state. Recently, it was reported that triphenylphosphane derivatives show AIE behavior in which they undergo potentially large structural changes in the excited state. Inspired by this report, photoinduced pyramidal inversion behavior of phosphanes was investigated. In photochemical experiments, the prepared P-stereogenic phosphanes exhibited photoracemization in dilute solution, and a negative correlation was observed between the photoracemization and the AIE phenomenon. Theoretical computations revealed that the inversion barrier in the excited state was much smaller than that in the ground state. This is the first report on the photoinduced pyramidal inversion behavior of phosphanes, which will provide new and unexplored applications.     

Synthesis of nonplanar bipyridyls bridged by disilane and disiloxane and their phosphorescent copper complexes

Disilane- and disiloxane-bridged bipyridyls ( DSBPy and DSOBPy ) were prepared and their optical properties were investigated in comparison with those of previously reported monosilane- and monogermane-bridged counterparts. The UV–visible absorption and photoluminescence bands of DSBPy and DSOBPy were blue-shifted as a result of elongation of the bridging units from monosilane and monogermane to disilane and disiloxane, likely due to the enhanced twisting of the bipyridyl units. Phosphorescent complexes DSBPy–Cu and DSOBPy–Cu were prepared by the interaction of DSBPy and DSOBPy with Cu₂I₂(PPh₃)₂. X-ray diffraction studies of their single-crystal structures revealed polymeric structures composed of repeat units of DSBPy or DSOBPy and [Cu^II(PPh₃)]₂. Organic light-emitting diodes with the ITO/PEDOT:PSS/ DSBPy–Cu or DSOBPy–Cu :PCTSQ/TAZ/Al structure were fabricated to examine the applications of the complexes as electroluminescent materials. The devices emitted yellow light with emission maxima at approximately 600 nm, and maximal luminance reached 120 and 190 cd m⁻² for devices based on DSBPy–Cu and DSOBPy–Cu , respectively. The performance of the DSOBPy–Cu -based device was improved by using TAZ as the dopant of the emissive layer, and luminance was increased to 390 cd m⁻².     

Mechanisms of Microscopic Displacement During Enhanced Oil Recovery in Mixed-Wet Rocks Revealed Using Direct Numerical Simulation

Transport in Porous Media - We demonstrate how to use numerical simulation models directly on micro-CT images to understand the impact of several enhanced oil recovery (EOR) methods on microscopic...     

15-deoxy-isoxeniolide-A,new diterpenoid from a bornean soft coral,Xenia sp.

A new xenicane diterpenoid, 15-deoxy-isoxeniolide-A (1) along with four known compounds 9-deoxy-isoxeniolide-A (2), isoxeniolide-A (3), xeniolide-A (4) and coraxeniolide-B (5) were isolated from the Bornean soft coral Xenia sp. The structures of these metabolites were elucidated on the basis of spectral analysis, NMR and HRESIMS. Compound 5 showed cytotoxic activity against ATL cell line, S1T.