Correlating the Surface Basicity of Metal Oxides with Photocatalytic Hydroxylation of Boronic Acids to Alcohols

Photoredox catalysis provides opportunities in harnessing clean and green resources such as sunlight and O₂, while the acid and base surface sites of metal oxides are critical for industrial catalysis such as oil cracking. The contribution of metal oxide surfaces towards photocatalytic aerobic reactions was elucidated, as demonstrated through the hydroxylation of boronic acids to alcohols. The strength and proximity of the surface base sites appeared to be two key factors in driving the reaction; basic and amphoteric oxides such as MgO, TiO₂, ZnO, and Al₂O₃ enabled high alcohol yields, while acidic oxides such as SiO₂ and B₂O₃ gave only low yields. The reaction is tunable to different irradiation sources by merely selecting photosensitizers of compatible excitation wavelengths. Such surface complexation mechanisms between reactants and earth abundant materials can be effectively utilized to achieve a wider range of photoredox reactions.     

Tertiary‐Alcohol‐Directed Functionalization of Remote C(sp3)−H Bonds by Sequential Hydrogen Atom and Heteroaryl Migrations

Reported for the first time is a tertiary‐alcohol‐guided heteroarylation of remote C(sp³)?H bonds. The mild and direct generation of alkoxyl radicals from alcohols is enabled by visible‐light photocatalysis. A remote hydrogen atom and heteroaryl migration sequence are involved in the reaction. Many sensitive groups remain intact in the reaction, thus illustrating wide functional‐group compatibility. This protocol provides a practical strategy for the late‐stage modification of alkyl ketones.     

Synthesis of Difluoromethylthioesters from Aldehydes

Difluoromethylthioester compounds are yet another important kind of organofluorine compound and are reported here for the first time. They can be efficiently synthesized from various aldehydes. The synthetic method features mild reaction conditions, good tolerance of functional groups, broad substrate scope, and importantly, no metal is involved in the reaction. The approach has the potential to become an important tool for the late‐stage functionalization of advanced synthetic intermediates, and should have many applications in medicinal chemistry.     

Fluorescence quenching and molecular docking study on the binding of four hydroxyanthraquinones to FTO

In this work, the binding of four hydroxyanthraquinones (HAQs) to fat mass and obesity-associated (FTO) protein has been studied using fluorescence, UV-vis absorption and circular dichroism spectroscopy as well as molecular docking analysis. Analysis of fluorescence data showed that the binding of HAQs to FTO occurred via a static quenching mechanism. Thermodynamic analysis and molecular docking results suggested that hydrophobic force played a major role in stabilising the HAQ-FTO complex. Circular dichroism spectra indicated that the secondary structure of FTO was changed by the addition of HAQs. Results also showed that emodin had the strongest quenching and binding ability among four HAQs.     

Fe-based metal-organic frameworks for the synthesis of N-arylsulfonamides via the reactions of sodium arylsulfinates or arylsulfonyl chlorides with nitroarenes in water

A newly developed chemoselective reaction of sodium arylsulfinates or arylsulfonyl chlorides with nitroarenes has been disclosed. The chemistry, in which non-toxic water and recyclable iron-based metal-organic frameworks are employed as the solvent and catalyst, respectively, provides an efficient approach for the generation of N-arylsulfonamides, which are widely present in biologically active compounds and drugs, rendering this methodology attractive to both synthetic and medicinal chemistry.     

新金鸡纳生物碱衍生物配体的合成及其在烯烃的不对称双羟化反应中的应用

以简便的方法高产率地合成四种金鸡纳生物碱的对甲苯磺酸酯类配体，并将其应用于烯烃的不对称双羟化反应中，取得了较好的不对称诱导效果，双羟化反应的化学产率为82％～95％，对映体过量最高达93％ee．     

First-principles study of methanol adsorption on heteroatom-doped phosphorene

First-principles calculations were firstly employed to investigate the adsorption of methanol on pristine and X-doped phosphorene (X=B, C, N and O). The N and O doping improved the adsorption of phosphorene with CH₃OH gas molecule, while B and C doping were almost not beneficial.     

Synthesis and crystal structures of two nickel coordination polymers generated from asymmetric malate ligand

Two nickel coordination polymers [Ni(H₂O)(C₄H₄O₅)]·H₂O 1 and [Ni(H₂O)(mal)(phen)] 2, have been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Crystal data for 1: C₄H₈O₇Ni, monoclinic Cc, , , , , Z=4. Crystal data for 2: C₁₆H₁₄N₂O₆Ni, orthorhombic Pna2₁, , , , Z=4. Compound 1 is constructed from [Ni(H₂O)(C₄H₄O₅)] sheets pillared through β-carboxylate groups into a 3D framework, which exhibits a diamond-like network. Compound 2 exhibits a 3D supramolecular network. To our knowledge, compound 1 represents the first diamond-like topology in the system of metal-malate. Other characterizations by elemental analysis, IR and TG are also described. The magnetic behavior of compound 1 has been studied.     

Activity of acetamide in acetamide-calcium nitrate melt solutions

Activity coefficients of acetamide in acetamide-calcium nitrate melt solutions were determined from cryoscopic data in the concentration range O to 0.151 mole fraction of calcium nitrate. Enthalpies of melting and melting point depressions were obtained from DSC measurements. Melt solutions were obtained from two crystalline forms of acetamide. Eutectic formation was observed in both crystalline forms. Heat capacity of pure acetamide in the two forms was measured in the temperature range 20 to 100°C. Activity coefficients obtained for molten acetamide from two sets of cryoscopic data were in good agreement. Change of activity coefficients with calcium nitrate concentration indicate strong association between solvent and solute and water-like acting of molten acetamide.