Kinetic Resolution of Racemic Allylic Alcohols by Catalytic Asymmetric Substitution of the OH Group with Monosubstituted Hydrazines

A new strategy has been established for the kinetic resolution of racemic allylic alcohols through a palladium/sulfonyl‐hydrazide‐catalyzed asymmetric OH‐substitution under mild conditions. In the presence of 1 mol % [Pd(allyl)Cl]₂, 4 mol % (S)‐SegPhos, and 10 mol % 2,5‐dichlorobenzenesulfonyl hydrazide, a range of racemic allylic alcohols were smoothly resolved with selectivity factors of more than 400 through an asymmetric allylic alkylation of monosubstituted hydrazines under air at room temperature. Importantly, this kinetic resolution process provided various allylic alcohols and allylic hydrazine derivatives with high enantiopurity.     

Surface modification of polyolefin separators for lithium ion batteries to reduce thermal shrinkage without thickness increase

Surface chemical modification of polyolefin separators for lithium ion batteries is attempted to reduce the thermal shrinkage, which is important for the battery energy density. In this study, we grafted organic/inorganic hybrid crosslinked networks on the separators, simply by grafting polymerization and condensation reaction. The considerable silicon-oxygen crosslinked heat-resistance networks are responsible for the reduced thermal shrinkage. The strong chemical bonds between networks and separators promise enough mechanical support even at high temperature. The shrinkage at 150 C for 30 min in the mechanical direction was 38.6% and 4.6% for the pristine and present graft-modified separators, respectively. Meanwhile, the grafting organic-inorganic hybrid crosslink networks mainly occupied part of void in the internal pores of the separators, so the thicknesses of the graft-modified separators were similar with the pristine one. The half cells prepared with the modified separators exhibited almost identical electrochemical properties to those with the commercial separators, thus proving that, in order to enhance the thermal stability of lithium ion battery, this kind of grafting-modified separators may be a better alternative to conventional silica nanoparticle layers-coated polyolefin separators.     

A Pronounced Halogen Effect on the Organogelation Properties of Peripherally Halogen Functionalized Poly(benzyl ether) Dendrons

An interesting halogen‐substituent effect on the organogelation properties of poly(benzyl ether) dendrons is reported. A new class of poly(benzyl ether) dendrons with halo substituents decorating their periphery was synthesized and fully characterized. A systematic study on the gelation abilities, thermotropic behaviors, aggregated microstructures, and mechanical properties of self‐assembled organogels was performed to elucidate the halogen‐substituent effects on their organogelation propensity. It was found that the exact halogen substitutions on the periphery of dendrons exert a profound effect on the organogelation propensity, and dendrons G _n ‐Cl (n=2, 3) and G₂‐I proved to be highly efficient organogelators. The cooperation of multiple π–π, dispersive halogen, CH–π, and weak C?H ??? X hydrogen‐bonding interactions were found to be the key contributor to forming the self‐assembled gels. Dendritic organogels formed from G _n ‐Cl (n=2, 3) in 1,2‐dichloroethane exhibited thixotropic‐responsive properties, and such thixotropic organogels are promising materials for future research and applications.     

Microtextures Induced by Nanosecond Laser on Ni–Co Alloy Coatings

Ni–Co alloys have a wide range of applications in various fields owning to their excellent physical, chemical, and mechanical properties. In this paper, we prepare Ni–Co alloy coatings on 316L stain steel surfaces by electroplating. We present a novel approach utilizing a nanosecond laser to induce microtextures on Ni–Co alloy coatings. We study experimentally the effects of laser power and scanning rate on the surface morphologies of Ni–Co alloy coatings. The results indicate that the shape and size of induced microtextures can be controlled by the laser power and scanning rate. The size of grains increases with increase in the work current of the laser (WCL) at a certain scanning rate. With the WCL constant, the size of grains decreases with increase in scanning rate while their average height increases. It is a simple and easily-controlled method for the fabrication of microstructures on Ni–Co alloy coatings, which has promising applications in investigations of the properties of microtextured surfaces, such as friction, adhesion, and wetting.     

Generation of Oxazolidine‐2,4‐diones Bearing Sulfur‐Substituted Quaternary Carbon Atoms by Oxothiolation/Cyclization of Ynamides

A novel method for metal‐free oxothiolation of ynamides to construct oxazolidine‐2,4‐diones bearing sulfur‐substituted quaternary carbon atoms has been developed. It represents a rare C?O bond cleavage of ynamides, as well as a facile and tandem approach for the formation of C?O, C?S, and C?Cl bonds. This redox‐neutral protocol can be applied to the synthesis of multisubstituted oxazolidine‐2,4‐diones with good chemoselectivity and good yields of isolated products under mild conditions.