Atroposelective Sulfenylation of Biaryl Anilines Catalyzed by Chiral SPINOL-Derived Selenide.

The atroposelective electrophilic sulfenylation of biaryl anilines has been realized for the first time. The reaction is enabled by a new chiral 6,6'-dianisole substituted SPINOL-derived selenide. A variety of axially chiral sulfur-containing biaryl aniline compounds were obtained in moderate to excellent yields with moderate to excellent enantioselectivities.

Nanoreactor Based on Cyclodextrin for Direct Electrocatalyzed Ammonia Synthesis.

The high-efficiency transition metal-free electrocatalytic nitrate reduction reaction (NORR) for ammonia synthesis has received more attention because of its green and environmentally friendly characteristics. Here, we report an efficient electrochemical NH synthesis directly from purely organic macrocyclic compounds α-, β-, and γ-cyclodextrins (CDs)-catalyzed transition metal-free electroreduction of nitrate under ambient conditions. In comparison with α-, and β-CDs, parent γ-CD presented uncommon catalytic performance with a relatively higher NH yield that can reach up to 2.

Reversible Emitting Anti-Counterfeiting Ink Prepared by Anthraquinone-Modified -Cyclodextrin Supramolecular Polymer.

Intelligent fluorescent materials have been paid more and more attention due to their wide application in information encryption and anti-counterfeiting materials. Herein, a supramolecular polymer is constructed through the host-guest interaction of anthraquinone-modified -cyclodextrin (AQ--CD) in aqueous solution. Thanks to the hydrophobic microenvironment of the cyclodextrin cavity and the shielding effect on oxygen molecules, the anthraquinone group, as the guest molecule, can rapidly produce 9,10-anthracenediol (QH) with strong fluorescence by photoreduction.

Metal-Organic Framework-Derived ZnO/ZnS Heteronanostructures for Efficient Visible-Light-Driven Photocatalytic Hydrogen Production.

Developing highly active, recyclable, and inexpensive photocatalysts for hydrogen evolution reaction (HER) under visible light is significant for the direct conversion of solar energy into chemical fuels for various green energy applications. For such applications, it is very challenging but vitally important for a photocatalyst to simultaneously enhance the visible-light absorption and suppress photogenerated electron-hole recombination, while also to maintain high stability and recyclability. Herein, a metal-organic framework (MOF)-templated strategy has been developed to prepare heterostructured nanocatalysts with superior photocatalytic HER activity.

Computational Discovery of Potent and Bioselective Protoporphyrinogen IX Oxidase Inhibitor via Fragment Deconstruction Analysis.

Tuning the binding selectivity through appropriate ways is a primary goal in the design and optimization of a lead toward agrochemical discovery. However, how to achieve rational design of selectivity is still a big challenge. Herein, we developed a novel computational fragment generation and coupling (CFGC) strategy that led to a series of highly potent and bioselective inhibitors targeting protoporphyrinogen IX oxidase.

Combined experimental and theoretical studies of regio- and stereoselectivity in reactions of β-isoxazolyl- and β-imidazolyl enamines with nitrile oxides.

Reactions of β-azolyl enamines and nitrile oxides were studied by both experimental and theoretical methods. ()-β-(4-Nitroimidazol-5-yl), (5-nitroimidazol-4-yl) and isoxazol-5-yl enamines smoothly react regioselectively at room temperature in dioxane solution with aryl, pyridyl, and cyclohexylhydroxamoyl chlorides without a catalyst or a base to form 4-azolylisoxazoles as the only products in good yields. The intermediate 4,5-dihydroisoxazolines were isolated as isomers during the reaction of ()-β-imidazol-4-yl enamines with aryl and cyclohexylhydroxamoyl chlorides.

Thermodynamics and kinetics of the hydride-transfer cycles for 1-aryl-1,4-dihydronicotinamide and its 1,2-dihydroisomer.

Five 1-(p-substituted phenyl)-1,4-dihydronicotinamides (GPNAH-1,4-H(2)) and five 1-(p-substituted phenyl)-1,2-dihydronicotinamides (GPNAH-1,2-H(2)) were synthesized, which were used to mimic NAD(P)H coenzyme and its 1,2-dihydroisomer reductions, respectively. When the 1,4-dihydropyridine (GPNAH-1,4-H(2)) and the 1,2-dihydroisomer (GPNAH-1,2-H(2)) were treated with p-trifluoromethylbenzylidenemalononitrile (S) as a hydride acceptor, both reactions gave the same products: pyridinium derivative (GPNA(+)) and carbanion SH(-) by a hydride one-step transfer. Thermodynamic analysis on the two reactions shows that the hydride transfer from the 1,2-dihydropyridine is much more favorable than the hydride transfer from the corresponding 1,4-dihydroisomer, but the kinetic examination displays that the former reaction is remarkably slower than the latter reaction, which is mainly due to much more negative activation entropy for the former reaction.