离子液体催化CO2与环氧化物合成环状碳酸酯

综述了离子液体催化CO2与环氧化物的环加成反应制备环状碳酸酯的研究进展。目前报道的离子液体主要包括咪唑盐、季铵盐、季鏻盐等。对比了传统离子液体与功能化离子液体对CO2环加成反应的催化活性、选择性以及催化作用机制。与传统的离子液体相比,功能化离子液体的羟基或羧基等官能团与卤素离子等Lewis碱之间存在协同效应,使得其对CO2与环氧化物的环加成反应具有更好的催化活性;将功能化离子液体固载于无机材料(SiO2,SBA-15,MCM-41等)或聚合物所得的多相催化剂不仅保持了官能团与阴离子之间的协同效应,而且载体与离子液体活性组分之间也显示出协同效应,使得该类催化剂具有很好的催化活性,稳定性好,可以多次重复使用,具有较好的工业化前景,是值得深入研发的一类催化材料。此外,离子液体对于手性环状碳酸酯的合成也具有较好的催化活性和立体选择性。     

阳离子光引发剂[CpFe(η6-tol)]BF4光聚合活性及增感的研究

研究了阳离子光引发剂[CpFe(η⁶-tol)]BF₄引发脂环族环氧树脂ERL-4221阳离子光聚合的活性.其响应峰在 374nm和 450nm处,大于二甲苯基碘盐的240nm,具有更高的感度.同时,研究了一些不同种类的过氧化物对[CpFe(η⁶-tol)]BF₄的增感作用,敏化效果与其氧化性一致:过氧化羟基异丙苯(CHP)≈过氧化苯甲酰 (BPO) >过氧化二异丙苯 (DCP),研究了光敏体系的紫外吸收光谱和荧光发射光谱,对增感机理作出初步解释.     

Multinuclear cobalt–salen complexes with phenylene linker for epoxide polymerizations

Di‐ and trinuclear cobalt (Co)–salen complexes with a benzene ring as a rigid linker were explored for epoxide polymerizations. The dinuclear Co–salen complex with a 1,2‐phenylene linker showed higher catalytic activity than the dinuclear Co–salen complex with a 1,3‐phenylene linker and the trinuclear Co–salen complex with a 1,3,5‐benzenetriyl linker for the copolymerization of propylene oxide (PO) with carbon dioxide. A combination of the absolute configuration of the two Co–salen moieties was found to affect its catalytic activity. The optimized dinuclear Co–salen complex with a heterochiral combination demonstrated highest activity and maintained its catalytic activity under a low catalyst concentration. The heterochiral dinuclear Co–salen complex also showed high activity for the copolymerization of PO with cyclic anhydride. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2150–2159     

A short and concise route to total synthesis of Dendrodolide L

A short and efficient method for the stereoselective synthesis of Dendrodolide L has been developed from inexpensive and commercially available starting material. This convergent synthesis utilizes Jacobsen kinetic resolution, regioselective ring-opening of epoxide and Yamaguchi macrolactonization as key steps.     

Conversion of carbon dioxide to cyclic carbonates using diimine Ru(II) complexes as catalysts

Cationic diimine Ru(II) complexes were synthesized and tested as catalysts for the formation of cyclic organic carbonates from CO₂ and liquid epoxides (propylene oxide, epichlorohydrine, 1,2‐epoxybutane and styrene oxide) which served as both reactant and solvent. The reaction rates not only depended on the type of ligand, but also on reaction conditions such as temperature, pressure, base, the epoxide substrates and the use of an additional solvent. Reaction rates in terms of turnover frequencies up to 4050 mol_product mol_cat.^?1 h^?1 at 99% selectivity were achieved by optimizing the diimine ligand as well as the reaction temperature and CO₂ pressure. Consistent with CV measurements, the electron donating group on the p‐position of the aryl ring accelerated the reaction rate. Copyright © 2008 John Wiley & Sons, Ltd.     

S-烷基异硫脲盐作为硫醇替代物经环氧开环反应合成β-羟基硫化物

S-烷基异硫脲盐作为一种无毒、无味、易于制备的硫醇替代物，在碱性水介质中、室温下与多种环氧化合物发生环氧开环反应，区域选择性、高收率地合成了一系列β-羟基硫化物。     

Synthesis of Amphiphilic Amino Alcohols

An efficient and general approach for the synthesis of amphiphilic 1,2-amino alcohols is reported. The use of N-benzyl protecting groups is essential for obtaining good yields when opening a long-chain terminal epoxide with an amine.     

Studies on PNPP Hydrolysis Catalyzed by Divalent Metal Ion Macrocyclic Schiff Base Complexes in Micellar Solution

Two transitional metal ion macrocyclic Schiff base complexes, NiL and CuL were synthesized and characterized, and the metallomicelles made up of the nickel(II) and copper(II) complexes and surfactants(LSS, Brij35, CTAB), as mimic hydrolytic metalloenzyme, were used in catalytic hydrolysis of carboxylic ester (PNPP). The analysis of specific absorption spectrums of the hydrolytic reaction systems indicates that key intermediates, made up of PNPP and Ni(II) or Cu(II) complexes, have formed in the reaction processes of the PNPP catalytic hydrolysis. In this, based on the analytic result of specific absorption spectrum, the mechanism of PNPP catalytic hydrolysis has been proposed; a kinetic mathematical model, applied to the calculation of the kinetic parameter of PNPP catalytic hydrolysis has been established on the foundation of the mechanism proposed; the acid effect of reaction system, structure effect of the complexes, effect of temperature and effects of micelle on the rate of PNPP hydrolysis catalyzed by the complexes also have been discussed.     

Fatty acid amide hydrolase inhibitors. 2. Novel synthesis of sterically hindered azabenzhydryl ethers and an improved synthesis of VER-156084

We report an improved synthesis of the fatty acid amide hydrolase (FAAH) inhibitor VER-156084. The key step is a novel, environmentally benign etherification to form an unusual, highly hindered azabenzhydryl ether. The method is applied to a variety of primary and secondary alcohols.