A new filled function method for an unconstrained nonlinear equation

In this paper, we transform an unconstrained system of nonlinear equations into a special optimization problem. A new filled function is constructed by employing the special properties of the transformed optimization problem. Theoretical and numerical properties of the proposed filled function are investigated and a solution of the algorithm is proposed. Under some conditions, we can find a solution or an approximate solution to the system of nonlinear equations in finite iterations. The implementation of the algorithm on six test problems is reported with satisfactory numerical results.     

Palladium-catalyzed desulfitative arylation of azoles with arylsulfonyl hydrazides

Palladium-catalyzed desulfitative and denitrogenative arylation of azoles with arylsulfonyl hydrazides has been achieved. A broad scope of azoles and arylsulfonyl hydrazides has been used to produce arylated azoles in high yields.     

以羰基磷氧化物为配体的铜催化的C-S偶联反应

以邻溴苯甲醛为原料合成了一系列的羰基磷氧化物,用作铜催化的C-S偶联反应的新配体.在较温和的反应条件下可成功催化碘代芳烃或溴代芳烃与硫醇的偶联反应,收率最高达99%.     

基于局部self-concordant障碍函数的全牛顿步多项式时间算法

由Nesterov和Nemirovski[4]创立的self-concordant障碍函数理论为解线性和凸优化问题提供了多项式时间内点算法.根据self-concordant障碍函数的参数,就可以分析内点算法的复杂性.在这篇文章中,我们介绍了基于核函数的局部self-concordant障碍函数,它在线性优化问题的中心路径及其邻域内满足self-concordant性质.通过求解此障碍函数的局部参数值,我们得到了求解线性规划问题的基于此局部Self-concordant障碍函数的纯牛顿步内点算法的理论迭代界.此迭代界与目前已知的最好的理论迭代界是一致的.     

Concise synthesis of novel practical sulfamide-amine alcohols for the enantioselective addition of diethylzinc to aldehydes

Novel sulfamide-amine alcohol ligands were designed using a grafting strategy and synthesized from readily available starting materials via a simple, efficient method. The key features of these ligands for the asymmetric addition of diethylzinc to aldehydes included stability, enhanced effectiveness without using Ti(O(i)Pr)(4), suitability for a variety of aldehydes, the ability to operate at room temperature, and selectability to afford either absolute configuration products with enantiomeric excess up to >99%.     

Silica modified with a thiourea derivative as a new stationary phase for hydrophilic interaction liquid chromatography

Nowadays there are limited types of commercially available stationary phases for hydrophilic interaction liquid chromatography and therefore new ones with unique selectivity are urgently in demand to meet the need of separations of various polar and hydrophilic analytes. The present study describes the preparation and evaluation of a new stationary phase based on thiourea derivative modified silica for hydrophilic interaction liquid chromatography. Thiourea derivative was bonded onto the surface of silica particles via a mild addition reaction between –NH₂ and –SCN, and the result of elemental analysis together with infrared analysis and solid‐state NMR spectroscopy proved that the synthesis method was feasible. The new stationary phase succeeded in fast separations of a wide range of polar and hydrophilic analytes and exhibited excellent separation performance, especially unique selectivity. Furthermore, the effects of water content, buffer pH, and salt concentration on retention indicated that a complicated separation mechanism rather than partitioning was involved in the stationary phase and hydrogen bonding interaction between analytes and thiourea functional group could play a very important role in its selectivity. For sure, the new stationary phase is of a great potential as a new type of hydrophilic interaction liquid chromatographic stationary phase.     

木糖醇和麦芽糖醇型亲水作用色谱固定相的制备及其分离性能的评价

利用-NCO和-OH的加成反应,通过简单的两步反应将木糖醇和麦芽糖醇成功地键合于硅胶表面,制备了两种新型糖醇类亲水作用色谱固定相。流动相中乙腈含量对保留的影响曲线表明,这两种糖醇固定相具有典型的亲水作用色谱固定相性质,对极性和亲水性化合物有很强的保留作用。利用这两种固定相成功分离了水溶性维生素、水杨酸及其类似物、碱基及其相应的核苷和淫羊藿苷类似物等模型混合物,同时糖醇固定相展现了新颖的选择性,特别是相对于线形的木糖醇键合固定相,非线形的麦芽糖醇键合固定相表现出了对糖基的独特保留能力。此外,缓冲盐的pH和浓度对保留的影响表明静电作用在这两种糖醇固定相的保留机理中也发挥着一定的作用。本文所发展的糖醇类固定相具有良好的分离性能,有望在亲水作用色谱分离领域发挥潜在的应用价值。     

Construction of Bridged Benzazepines via Photo-Induced Dearomatization

Bridged benzazepine scaffolds, possessing unique structural and physicochemical activities, are widespread in various natural products and drugs. The construction of these skeletons often requires elaborate synthetic effort with low efficiency. Herein, we develop a simple and divergent approach for constructing various bridged benzazepines by a photocatalytic intermolecular dearomatization of naphthalene derivatives with readily available α-amino acids. The bridged motif is created via a cascade sequence involving photocatalytic 1,4-hydroaminoalkylation, alkene isomerization and cyclization. Interestingly, the diastereoselectivity can be regulated through different reaction modes in the cyclization step. Moreover, aminohydroxylation and its further bromination have also been demonstrated to access highly functionalized bridged benzazepines. Preliminary mechanistic studies have been performed to get insights into the mechanism. This method provides a divergent synthetic approach for construction of highly functionalized bridged benzazepines, which have been otherwise difficult to access.     

过渡金属催化[2 + 2 + 2]环加成反应合成吡啶衍生物

环加成反应可以一步同时构建多个化学键,是目前国内外研究最为活跃的领域之一。相比于传统方法,过渡金属催化的[2+2+2]环加成反应是合成吡啶衍生物的有效手段。本文从反应机理、非手性吡啶化合物合成和手性吡啶化合物合成三个方面阐述了近年来吡啶衍生物的研究情况,涉及Co、Rh、Ru、Fe、Ni、Ti等金属催化体系。