具有生理活性的天然螺缩酮化合物研究进展

螺缩酮类化合物广泛存在于自然界中, 它们表现出的很好的生理活性已引起各国科学家的兴趣. 对近年来天然存在的螺缩酮化合物的研究进展进行了总结, 描述了这类化合物的结构特征, 展望了在医药、农药等方面的潜在发展前景.     

ZnCl2温和有效地催化活泼亚甲基化合物与苄醇或烯丙醇的 直接烷基化反应

报道了ZnCl2催化的活泼亚甲基化合物和苄醇或烯丙醇的直接烷基化反应. 在无水ZnCl2 (5～10 mol%)的催化下, 以二氯甲烷为溶剂, 活泼亚甲基化合物和苄醇或烯丙醇进行直接烷基化反应以较高的收率得到活泼亚甲基化合物的烷基化产物, 反应后处理简单, 说明ZnCl2是一种温和有效的活泼亚甲基化合物和苄醇或烯丙醇进行直接烷基化的催化剂. 并对反应的机理进行了初步研究.     

Synthesis and Crystal Structure of an Ionic Compound [Fe(CN)_6·(PhCH_2NC_9H_7)_4]·12H_2O

A novel ionic compound [Fe(CN)6(PhCH2NC9H7)4]·12H2O (C70H80FeN10O12, Mr = 1309.29) has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. The compound crystallizes in triclinic, space group P1, with a = 10.968(7), b = 11.466(7), c = 14.077(8) , α = 87.014(7), β = 78.124(7), γ = 72.708(7)o, V = 1654.1(17) 3, Z = 1, Dc = 1.314 g·cm–3, F(000) = 692, μ = 0.298 mm–1, the final R = 0.0519 and wR = 0.1355. The building unit of the title compound consists of four (PhCH2N+C9H7) ions, one [Fe(CN)6]4– anion, and a dozen water molecules. According to the structural analysis, [Fe(CN)6]4– ions are linked together by O–H···O and O–H···N hydrogen bonds, while (PhCH2N+C9H7) and [Fe(CN)6]4– ions interact with each other by electrostatic force to form an ionic compound.     

New Gilman-type lithium cuprate from a copper(II) salt: synthesis and deprotonative cupration of aromatics

Deprotonative cupration of aromatics including heterocycles (anisole, 1,4-dimethoxybenzene, thiophene, furan, 2-fluoropyridine, 2-chloropyridine, 2-bromopyridine, and 2,4-dimethoxypyrimidine) was realized in tetrahydrofuran at room temperature using the Gilman-type amido-cuprate (TMP)₂CuLi in situ prepared from CuCl₂·TMEDA through successive addition of 1 equiv of butyllithium and 2 equiv of LiTMP. The intermediate lithium (hetero)arylcuprates were evidenced by trapping with iodine, allyl bromide, methyl iodide, and benzoyl chlorides, the latter giving the best results. Symmetrical dimers were also prepared from lithium azine and diazine cuprates using nitrobenzene as an oxidative agent.     

Convenient and rapid synthesis of α-aminonitriles starting directly from nitro compounds in water

A distinct approach for the synthesis of α-aminonitriles has been discovered by three-component reaction of nitroarenes, aldehydes, and TMSCN using indium in dilute aqueous HCl at room temperature. The products were formed in high yields (86-96%) within a short period of time (5-20 min). This one-pot conversion consists of the following steps: (i) reduction of nitro compounds to amines, (ii) formation of imines from amines and aldehydes and (iii) addition of cyanide anion to the imines.     

2,2,3,3,11,11,12,12-Octamethyl-1,4,7,10,13-pentaoxacyclohexadecane: improved synthesis and crystal structure with NaSCN

An efficient synthesis of 2,2,3,3,11,11,12,12-octamethyl-1,4,7,10,13-pentaoxacyclohexadecane (1, OM16C5) is described, which affords over an order of magnitude improvement in yield over the previously reported method. The first X-ray crystal structure of 1, as a complex with NaSCN, is also reported.     

Vibrational CD spectroscopy as a powerful tool for stereochemical study of cyclophynes in solution

Stereochemical study of cyclophynes, which is otherwise rather difficult to perform, can be achieved by vibrational CD spectroscopy.     

五氧化二钒插层纳米复合材料的组装与电化学性能

五氧化二钒具有二维空间层状结构,层间伸缩性好,具有纳米尺寸,且有可做成无定形、高比表面积的溶胶.凝胶、干凝胶、气凝胶和类气凝胶等多种形态的优点.目前以其为主体的插层纳米复合材料研究十分活跃,本文综述了近年来合成的五氧化二钒插层化合物的组装及其电化学性能研究的进展.     

Zinc Hydrogensulfate as an Efficient Catalyst for Preparation of β-Amido Carbonyl Compounds

A one‐pot and efficient three‐component condensation of benzaldehyde derivatives, enolizable ketones or ketoesters, acetyl chloride, and acetonitrile or benzonitrile under ambient conditions in the presence of zinc hydrogensulfate for the synthesis of β‐amido carbonyl compounds is described. The simple experimental procedure, high to excellent yields of products and preparation of diastereoselective β‐acetamido ketoesters are strong features of the presented method.