芳酰胺类大环一步高效合成及其成环机理研究进展

总结了最近发现的新型芳酰胺及芳酰肼大环一步合成反应,着重探讨了由分子内三中心氢键所引导的高效一步成环反应机理.这类反应是由未成环寡聚物前体的折叠构象所构筑,不仅高效,而且反应机理新颖,提供了传统成环反应难以得到的几类刚性大环的合成方法.这些大环化合物表现出对客体识别的高度专一性,并能形成具有高通量性的跨膜孔道.     

Microwave-Assisted Synthesis of Aryl Amide Bonds on Solid Phase

A novel microwave-assisted synthesis of a library of triarylamides has been undertaken on the solid-phase.     

含四硫富瓦烯大环化合物的合成与研究进展

简要介绍了含有四硫富瓦烯(TTF)单元的大环化合物的分类, 概括了各类含四硫富瓦烯大环化合物的合成方法, 主要包括含有1,3-二硫杂环戊烯-2-硫酮单元的大环化合物在亚磷酸三烷基酯参与下的偶合反应, 以及带有氰乙基硫等取代基的预先合成的官能化TTF与二卤代低聚醚的反应. 综述了含四硫富瓦烯大环化合物的电化学性能及其在分子识别方面应用研究的最新进展, 提出了含四硫富瓦烯大环化合物的发展趋势.     

Lanthanide SMMs Based on Belt Macrocycles: Recent Advances and General Trends

Enhancement of axial magnetic anisotropy is the central objective to push forward the performance of Single-Molecule Magnet (SMM) complexes. In the case of mononuclear lanthanide complexes, the chemical environment around the paramagnetic ion must be tuned to place strongly interacting ligands along either the axial positions or the equatorial plane, depending on the oblate or prolate preference of the selected lanthanide. One classical strategy to achieve a precise chemical environment for a metal centre is using highly structured, chelating ligands. A natural approach for axial-equatorial control is the employment of macrocycles acting in a belt conformation, providing the equatorial coordination environment, and leaving room for axial ligands. In this review, we present a survey of SMMs based on the macrocycle belt motif. Literature systems are divided in three families (crown ether, Schiff-base and metallacrown) and their general properties in terms of structural stability and SMM performance are briefly discussed.     

Synthesis and Structure Elucidation of Large Phosphorus Macrocycles

The simple reaction between 1,ω-diamino derivatives and R-bis-(dimethylamino)-phosphane (R = CH₃, C₆H₅), followed by an oxidation step led to the formation of the expected macrocyclic phosphorus compounds. By this way 17- to 27-membered macrocycles were easily obtained. During the synthesis, the formation of dimeric (40- and 52-membered rings) and trimeric (78-membered rings) macrocyclic species were obtained from 3 and 5 and fully characterized by NMR and mass spectrometry. The P(III) phosphorus species exchange in solution and the macrocycle/oligomers ratio is temperature and concentration dependent. The crystal structure analysis of macrocycles 1, 5, 7 and 8 show that voids are minimized in the solid so that the macrocyclic cavity is filled up with part of the molecule itself or with a guest molecule, when the size of the macrocycle does not allow molecular folding for self-filling the cavity. Dedicated to the memory of Prof. Jean-Bernard Robert     

微波辅助组合合成的研究进展

微波辅助组合合成技术是近年来发展起来的一种新的制备化合物库的组合化学技术, 它不仅可以克服传统固相组合合成技术以及液相组合合成技术无法提高产物收率的不足, 而且利用该技术所制得的化合物库中对应的是高纯度的单一化合物, 采用高通量筛选技术可以快速直接地确定高活性结构, 极大地提高了新药开发的效率. 主要就近年来微波辅助组合合成技术的研究进展情况进行介绍, 内容包括固相组合合成、基于聚合物支载的催化剂的组合合成、液相组合合成、氟相组合合成以及组合平行合成等.     

Microwave-Assisted Synthesis of P-Heterocycles*

Abstract

The direct esterification, thioesterification and amidation of cyclic phosphinic acids, such as 1-hydroxy-3-phospholene 1-oxides, 1-hydroxy-phospholane 1-oxides and a 1-hydroxy-1,2,3,4,5,6-hexahydrophosphinine 1-oxide, which do not take place on conventional heating, were carried out under MW conditions in excess of the alcohol, thioalcohol and amine, respectively. The cyclic phosphinates were also prepared by MW-assisted alkylating esterification of the corresponding phosphinic acids in solid–liquid phase. Using alkyl halides of normal reactivity, the application of a phase transfer catalyst was also beneficial. In addition, MW-assisted Diels–Alder reactions, so-called inverse Wittig-type reactions furnishing β-oxophosphoranes, a few kinds of phospha-Michael additions leading to precursors of bidentate P-ligands, and a few Kabachnik–Fields condensations affording α-aminophosphonates and α-aminophosphine oxides are discussed.     

Recent Advances in the Synthesis and Applications of Nitrogen-Containing Macrocycles

Macrocyclic nitrogen-containing compounds are versatile molecules. Supramolecular, noncovalent interactions of these macrocycles with guest molecules enables them to act as catalysts, fluorescent sensors, chiral or nonchiral selectors, or receptors of small molecules. In the solid state, they often display a propensity to form inclusion compounds. All of these properties are usually closely connected with the presence of nitrogen atoms in the macrocyclic ring. As most of the reviews published so far on macrocycles were written from the viewpoint of functional groups, synthetic methods, or the structure, search methods for literature reports in terms of the physicochemical properties of these compounds may be unobvious. In this minireview, the emphasis was put on the synthesis and applications of nitrogen-containing macrocyclic compounds, as they differ from their acyclic analogs, and at the same time are the driving force for further research.     

Rapid Microwave-Assisted Synthesis of CdS/Graphene/MoSx Tunable Heterojunctions and Their Application in Photocatalysis

Nanoscale two-dimensional nanostructures have shown great potential as functional components in photocatalysis. Here, investigations on the synthesis of heterostructured hybrids, comprised of 0D CdS nanoparticles as semiconductor and 2D/2D graphene/MoS_x as co-catalyst, are reported. The approach involves a rapid microwave-assisted reaction in autoclave conditions, by adopting either a one-step or a two-step protocol. The chemical speciation of the nanocomposites was found to depend strongly on the compounding conditions of the precursor substances. The photocatalytic activity was assessed by monitoring the photodegradation rate of 4-nitrophenol in solution using simulated solar light irradiation. The photocatalytic activity of the hybrids may be attributed to a combination of beneficial characteristics, strongly related to the chemical speciation of the composite components. Moreover, intimate contacts of the latter result in efficient heterojunctions. Overall, the present study provides valuable insight into the development of functional heterostructured photocatalysts comprised of two-dimensional nanomaterials.     

含三螺吡喃单元大环分子的合成和酸致变色效应

合成了含有3个螺吡喃单元的大环分子,采用点击化学方法实现高效的闭环反应,大环分子产率为64%。 使用红外、核磁和质谱等方法检测和表征了反应中间产物和目标产物,质谱分析结果证实环化结构。 使用紫外-可见光谱仪观察到大环产物和线性螺吡喃前体分子在pH值接近4时的酸致变色效应。 与线性螺吡喃前体分子的最大紫外吸收峰位置（476 nm）相比,螺吡喃大环分子在最大紫外吸收峰位置（464 nm）发生蓝移。 螺吡喃大环分子比线性前体分子具有更大的摩尔消光系数,其pH响应性能更加优异。     

Synthesis of Some New Macrocyclic Bis-sulfonamides by Fast Addition Method

Novel macrocyclic bis-sulfonamides that structurally related to the proton-ionizable crown compounds have been synthesized. These compounds were obtained in the macrocyclization step by the fast addition method, and the results were compared with both high dilution and solvent-free conditions.     

潜在的大环锌金属蛋白酶抑制剂的设计与合成

A series of succinate-derived macrocyclic amides 1 were synthezized using ring-closing metathesis in the keystep.The substrate scope includes tings of 11 to 14 members.The cyclic dicarboxylic acids 1 represent a family ofnew model compounds for potential zinc metalloprotease inhibitors.The metathesis precursors were provided byamide coupling of tert-butyl 3-earboxyhex-5-enoate 2 with numerous side chain alkenylated amino acid esters ofgeneral type 3 derived from L-tyrosine and L-cysteine.     

芳炔类共轭大环化合物

芳炔类大环化合物是最近10年来新兴的一种富碳共轭大环状分子，迅速发展到 近100种，可在光、电、磁、纳米等功能材料中得到广泛应用，引起了人们极大的 兴趣，对芳炔类大环化合物的研究，特别是合成方法和性质进行了综述，并提出了 这一领域的发展方向和需要解决的重点课题。     

Interplay of Interactions Governing the Dynamic Conversions of Acyclic and Macrocyclic Helicates

Systemic change : A system of transformations between helical structures was observed to be governed by interactions mediated by the electronic effects of substituents, entropic effects, the conformational preferences of organic building blocks, and the coordinative preferences of the metal ion. All of these effects were important, but all must be considered together to allow the prediction of the product observed (see scheme).

     

One‐Pot Multimolecular Macrocyclization for the Expedient Synthesis of Macrocyclic Aromatic Pentamers by a Chain Growth Mechanism

POCl₃‐mediated one‐pot macrocyclization allows the highly selective formation of five‐residue macrocycles that are rigidified by internally placed intramolecular hydrogen bonds. Mechanistic investigation by using tailored competition experiments and kinetic simulation provides a comprehensive model, supporting a chain‐growth mechanism underlying the one‐pot formation of aromatic pentamers, whereby the successive addition of a bifunctional monomer unit onto either another monomer or the growing oligomeric backbone is faster than other types of bimolecular condensations involving oligomers longer than monomers. DFT calculations at the B3LYP/6‐31G* level reveal the five‐residue pentamer to be the most stable with respect to alternative four‐, six‐, and seven‐residue macrocycles. These novel mechanistic insights may become useful in analyzing other macrocyclization, oligomerization, and ploymerization reactions.     

Size-Induced Highly Selective Synthesis of Organometallic Rectangular Macrocycles and Heterometallic Cage Based on Half-Sandwich Rhodium Building Block

The controlled synthesis of organometallic supramolecular macrocycles cages remains interesting and challenging work in the field of supramolecular chemistry. Here, two tetranuclear rectangular macrocycles and an octuclear cage were designed and synthesized utilizing a rigid and functionalized pillar linker, 2,6-bis(pyridin-4-yl)-1,7-dihydrobenzo [1,2-d:4,5-d′]diimidazole (BBI4PY) based on three half-sandwich rhodium building blocks bearing different sizes. X-ray crystallography in combination with ¹H NMR spectroscopy elucidated that the two building blocks with shorter spacers only result in rectangular macrocycles. However, the building block of bulkier size to avoid the π-π stacking interactions between two ligands BBI4PY led to the formation of an octuclear cage complex. The latter cage contains two types of metal ions, namely Rh³⁺ and Cu²⁺, showing significant characteristics of heterogeneous metal-assembling compounds. In addition, the cage accommodates two free isopropyl ether solvent molecules, thus displaying host–guest behavior.     

Efficient Bromination of Naphthalene Dianhydride and Microwave-Assisted Synthesis of Core-Brominated Naphthalene Diimides

This article presents an efficient method for the synthesis of core-brominated naphthalene diimides (NDI) from naphthalene dianhydride (NDA). A procedure for monitoring the NDA bromination reaction by ¹H NMR spectroscopy is described, allowing for optimization and greater consistency of this reaction. Furthermore, the subsequent bis-imidization reaction of the brominated NDA product has been significantly enhanced using microwave-assisted conditions, with recovery of pure product via simple filtration in excess of 90% of theoretical yield. This chemistry offers greatly improved methodology for obtaining core-substituted NDI compounds with high efficiency and good yields.     

含吡啶-2,6-二酰亚胺单元的大环化合物合成及性质

在硫酸催化作用下,用前体二醛1[1,3-二(2'-甲酰苯氧基)丙烷]和前体二胺2[N,N'-(2-胺基苯基)-2,6-二甲酰亚胺吡啶]合成了[1+1]席夫碱大环化合物3,进一步还原得到饱和大环4。 用¹H NMR、IR、元素分析和质谱等技术手段对大环3和4的组成进行了表征。 采用X射线衍射仪测定了大环3 和4的晶体结构。 用UV-Vis光谱仪对大环3和4与系列阴离子的作用分别进行了考察,结果表明,饱和大环4仅对F^-有明显的选择性作用,并测定了该配位反应的配位比和平衡常数,进一步考察了大环3和4对甲醇的吸附性能。     

Efficient Construction and Structure Determination of Novel Macrocycles with Calixarene Bishydrazones

A series of large macrocyclic calixarene bishydrazones were efficiently synthesized by [2+2] condensation reactions of calix[4]arene 1,3‐disubstituted aldehydes with hydrated hydrazine. The X‐ray single crystal diffraction showed that macrocycles form a distinctive calixtube‐liking shape.     

芳香寡聚磺酸酯桥联大环化合物的合成和紫外光谱

以芳香二磺酰氯和芳香二酚为原料,三乙胺作缚酸剂,二氯甲烷作溶剂,采取一步成环法合成了一系列新型的、芳环单元不同的芳香寡聚磺酸酯桥联大环化合物。 合成产物的结构用IR、¹H NMR、¹³C NMR和MALDI-TOF等技术手段进行了确认。 并对合成方法、紫外光谱和变温核磁结构研究进行了有价值的探讨。 化合物3~5的DMF溶液的最大紫外吸收峰在266 nm处,化合物6在267 nm处,摩尔吸光系数分别是4.65×10⁴、5.61×10⁴、5.09×10⁴和9.98×10⁴ L/(mol·cm);检出限分别是2.15×10^-7、1.78×10^-7、1.96×10^-7和1.00×10^-7 mol/L。 变温核磁数据证明,苯环上连有支链有利于固定构象,可以通过这种方法合成结构固定的杯芳烃。