Atroposelective Access to 1,3-Oxazepine-Containing Bridged Biaryls via Carbene-Catalyzed Desymmetrization of Imines

We disclose herein an atroposelective synthesis of novel bridged biaryls containing medium-sized rings via N-heterocyclic carbene organocatalysis. The reaction starts with addition of the carbene catalyst to the aminophenol-derived aldimine substrate. Subsequent oxidation and intramolecular desymmetrization lead to the formation of 1,3-oxazepine-containing bridged biaryls in good yields and excellent enantioselectivities. These novel bridged biaryl products can be readily transformed into chiral phosphite ligands. Preliminary density function theory calculations suggest that the origin of enantioselectivity arises from the more favorable frontier molecular orbital interactions in the transition state leading to the major product.     

基于自适应混沌控制的外汇干预有效性研究

中央银行外汇干预的有效性一直是金融领域研究和争论的热点问题,并且至今尚未达成一致的结论,寻找科学的理论与方法对其做进一步的探讨具有重要意义。针对该问题提出一种新的解决方案,即在扩展Dorn-busch汇率模型基础上,运用自适应混沌控制方法指导外汇干预策略,试图通过检验干预是否能够控制汇率时间序列的混沌行为并最终达到稳定汇率的目的,来论证外汇干预的有效性。仿真结果表明,通过自适应地寻找合理的干预尺度,外汇干预行为最终能够成功地将汇率稳定在系统均衡水平上。研究成果不但为外汇干预有效性给出了理论支持,还为中央银行外汇干预策略的制定提供了参考。     

Positional Electronic Effects in Iminopyridine-N-oxide Nickel Catalyzed Ethylene Polymerization

Main observation and conclusionA series of dibenzhydryl-based iminopyridine-N-oxide ligands bearing a range of electron-donating or-withdrawing substituents(OM...     

False Discovery Variance Reduction in Large Scale Simultaneous Hypothesis Tests

Methodology and Computing in Applied Probability - Statistical dependence between hypotheses poses a significant challenge to the stability of large scale multiple hypotheses testing. Ignoring it...     

Effects of size and location of distal tear on hemodynamics and wave propagation in type B aortic dissection

Applied Mathematics and Mechanics - The type B aortic dissection (TBAD) is a perilous disease with high morbidity and mortality rates. The hemodynamics of TBAD in different scenarios has been...     

Precise Supramolecular Polymerization of Liquid Crystalline Block Copolymer Initiated by Heavy Metallic Salts

Chinese Journal of Polymer Science - Heavy metallic salts are capable to bind with proteins and cause detrimental fibrilization in living cells. Herein, we report a similar case of supramolecular...     

Alternating copolymerization of carbon monoxide and vinyl arenes using [N,N] bidentate palladium catalysts

The alternating copolymers of carbon monoxide (CO) and vinyl arene monomers, namely aromatic polyketones, are a family of attractive engineering plastic. In the catalytic synthesis of this kind of polymeric materials, [N,N] bidentate palladium catalysts represent the most successful catalytic systems. In this review, we introduce the present status of polyketone synthesis, with a focus on the aromatic polyketones made from vinyl arene and CO. We also address the palladium-catalyzed CO/vinyl arene alternating copolymerization mechanism. A variety of [N,N] bidentate palladium catalysts bearing 2,2′-bipyridine, 1,10-phenanthroline, α-diimine, and pyridine-imine ligands are surveyed for CO/vinyl arene copolymerization. The effects of vinyl arene monomer, counteranion, and solvent on copolymerization are also discussed. The copolymerization stereochemistry including chain end-control and enantiomorphic site control mechanisms is introduced. This review aims to promote the design of [N,N] bidentate palladium catalysts for CO/vinyl arene copolymerization for the development of high-performance aromatic polyketones.     

Efficient Pyrazolo[5,4-f]quinoxaline Functionalized Os(II) Based Emitter with an Electroluminescence Peak Maximum at 811 nm

Upon fusing the pyrazinyl pyrazole entity in giving pyrazolo[3,4-f]quinoxaline chelate, the corresponding Os(II) based NIR emitter exhibited “invisible” and efficient electroluminescence with a peak maximum at 811 nm. A maximum external quantum efficiency of 0.97 % and a suppressed efficiency roll-off till a current density of 300 mA cm⁻² was also exhibited.