含长链亚烷基桥的芳炔类共轭大环的合成

采用模板导向法高产率地合成了两个含长链亚烷基桥的芳炔类共轭大环. 通过四碘化合物与单保护双炔化合物的四重Hagiraha偶合反应构建了环化所需要的复杂前体. 通过相应的模板四炔衍生物的分子内Glaser 偶合反应环化得到大环. 大环的结构用NMR, GPC 及UV-Vis表征确证.     

基于席夫碱反应的共价有机骨架材料

席夫碱共价有机骨架材料（Schiff-base COFs）是根据Schiff-base反应原理缩合形成的一类COFs材料。Schiff-base COFs具有骨架密度低、比表面积大、孔径尺寸可控、有机单体种类丰富、合成方法灵活多样、表面化学性质可功能化,易于引入特定的分子识别位点,以及物理化学稳定性优异等特征。Schiff-base COFs在气体吸附/储存、传感、催化、光电材料和前处理介质等诸多领域有重要的应用前景,成为材料科学领域的研究热点。本文主要综述了近年来Schiff-base COFs材料的合成类型、制备方法,以及该材料在不同领域的应用研究进展。最后,总结了该材料的研究现状并展望了该研究领域未来的发展方向和应用前景。     

二联苯和氨基酸构建的大环化合物自组装研究

以二联苯作为模板,设计并合成了3个二联苯和氨基酸构建的大环化合物.晶体结构结果研究发现,在固态,这些大环化合物分别组装成了管状、三维网状和链状的超分子结构,其中,C-H…O氢键在维持这些大环的组装方面发挥了重要作用.这将有助于进一步增加对分子自组装、分子识别以及生物大分子的稳定性方面的理解.     

含有氢键供体大环化合物的构筑及其功能研究进展

含有氢键供体基团构筑的大环化合物因其结构中具有可以提供氢键供体的N—H基团,可以为大环化合物的主客体化学提供额外的分子间作用力,在分子识别、自组装以及超分子催化等领域被广泛应用.综述了近十年基于(硫)脲键、酰胺键构筑的大环化合物的合成方法及其在分子识别中的最新研究进展.为今后此类大环化合物的合成及应用提供参考.     

1,8-萘二酰亚胺与炔类的光化环加成反应

酰亚胺类化合物与烯烃的光化反应是有机光化学中的一个重要而活跃的领域.这些反应不仅对光化学的机理研究做出了很大贡献,而且在合成杂环以及中到大环化合物方面具有很高的合成价值.为了扩大这一领域的研究范围,我们把反应物从烯烃扩大至炔烃.本文报道1,8-萘二酰亚胺与炔类化合物的光化反应.     

含四元环的多环芳香化合物的研究进展

含四元环的多环芳香化合物通常能够表现出独特的光物理和化学性质,在很多领域具有潜在应用价值.分别针对线型、角型、螺旋型和环型含四元环多环芳香化合物的合成方法、分子堆积方式、光电性质及载流子迁移率等方面进行归纳总结.研究表明,表面合成法更利于制得规则形貌的多环芳香化合物;线型类分子表现出了较高的载流子迁移率;角型分子通常显...     

光催化苄基邻卤芳醚与CO2的连续去芳构化/羧化反应合成螺环羧酸(英文)

自1900年首次发现螺环化合物以来,由于它在药物分子、手性配体、激光染料等领域的重要作用,越来越多的螺环化合物被发现和研究.目前已研发出了几种典型的反应来合成螺环化合物,如分子间的环加成或偶联反应及双官能团化合物分子内的偶联反应.但这些方法仍存在选择性难以控制、螺环中官能团耐受性差、条件苛刻等不足.因此,有必要发展合成含各类官能团的螺环的方法.近年来,芳基化合物的分子内去芳构化已经成为合成螺环骨架的有效策略,尤其是通过光催化去芳构化合成螺环.CO₂作为C1合成子具有丰富、低成本、可持续及无毒等优势,若将CO₂作为羧酸源键联在螺环骨架上,将有可能构建具有潜在生物活性的螺环羧酸衍生物.基于本课题组对光催化CO₂转化利用反应的持续研究,本文设计开发了一种合成螺环羧酸化合物的便捷方法,即光催化苄基邻卤芳醚与CO₂的连续去芳构化/羧化反应.根据条件筛选实验结果,最终选择1,2,3,5-四(咔唑-9-基)-4,6-二氰基苯(4Cz IPN)作为光敏剂, N,N-二异丙基乙基胺(DIPEA)为还原剂,叔丁醇钠作为...     

通过环加成反应和串联反应构建桥环化合物的研究进展

桥环化合物广泛存在于天然产物和具有重要生理活性的分子中,在药物化学、天然产物化学、合成化学、材料化学及生命科学等领域具有重要的应用价值.近年来,经过广大化学工作者的不懈努力,己发展了系列高效构建桥环化合物的新方法.从环加成反应和串联反应两种策略出发,详细介绍近五年来用于构建桥环化合物的方法及最新研究进展,简要分析目前方...     

新型氮杂大环化合物的合成及其超分子识别性能

含氮杂芳环结构单元(如吡啶、吡唑或咪唑环等)的大环化合物,因其与金属离子形成具有特殊化学性能的配合物而被广泛研究并用于生物化学、药物化学、材料化学等领域.生命体系中的受体通常含有不同类型的配位部位,因而具有对不同底物的识别作用.设计合成含有不同配位原子和特定结构的大环化合物,对于模拟某些生命现象具有重要的研究意义.近年来开展的酶模型研究中,能对氨基酸进行有效手性识别和液膜传输的主体分子多为氮杂大环化合物.为此,本文合成了两种带有侧链功能基团和手性基团的氮杂大环化合物.     

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.     

图形软件与量化软件联合用于创建大环分子计算模型

通过实例介绍了将图形软件与量子化学计算软件联合用于创建大环分子量化计算模型的探索结果和操作步骤，为提高大环分子理论研究的工作效率提供了新的方法。     

Large ring-forming alkylations provide facile access to composite macrocycles

Macrocyclic compounds have potential to enable drug discovery for protein targets with extended, solvent-exposed binding sites. Crystallographic structures of peptides bound at such sites show strong surface complementarity and frequent aromatic side-chain contacts. In an effort to capture these features in stabilized small molecules, we describe a method to convert linear peptides into constrained macrocycles based upon their aromatic content. Designed templates initiate the venerable Friedel–Crafts alkylation to form large rings efficiently at room temperature – routinely within minutes – and unimpeded by polar functional groups. No protecting groups, metals, or air-free techniques are required. Regiochemistry can be tuned electronically to explore diverse macrocycle connectivities. Templates with additional reaction capabilities can further manipulate macrocycle structure. The chemistry lays a foundation to extend studies of how the size, shape and constitution of peptidyl macrocycles correlate with their pharmacological properties.     

Photoactive donor-acceptor conjugated macrocycles: New opportunities for supramolecular chemistry

The design and synthesis of photoactive macrocyclic molecules continue to attract attention because such species play important roles in supramolecular chemistry as well as photoelectronic applications. Donor-acceptor (D-A) conjugated macrocycles are an emerging class of photoactive molecules due to their D-A conjugated structural characteristics and tunable optical properties. In addition, the well-defined cavities in such D-A macrocycles endow them with versatile host-guest properties. In this review, we provide a comprehensive summary of D-A conjugated macrocycle chemistry, detailing recent progress in the area of synthetic methods, optical properties, host-guest chemistry and applications of the underlying chemistry to chemical sensors, bioimaging and photoelectronic devices. Our objective is to provide not only a review of the fundamental findings, but also to outline future research directions where D-A conjugated macrocycles and their constructs may have a role to play.     

Structure-directing role of molecules containing benzyl rings in the synthesis of a large-pore aluminophosphate molecular sieve: an experimental and computational study

We describe the synthesis of AlPO-5 and SAPO-5 materials (AFI topology) using five different tertiary amines or quaternary ammonium ions containing one or two benzyl rings as structure-directing agents (SDAs). All of the molecules successfully direct the crystallization of AlPO-5; however, only the most efficient templates are able to crystallize SAPO-5. The observed differences in template efficiency can be rationalized in terms of the interaction energy between these molecules and the AFI framework. In ranking the template molecules, we notice that a well-defined molecular shape enhances the templating ability, but molecules that are too rigid are not able to adapt to the AlPO framework, yielding an inferior templating ability. Results of atomic-level modeling show that templates with one benzyl ring self-assemble in the main AFI channel by forming dimers with the benzyl rings parallel to each other; templates with two benzyl rings assemble instead into longer chains in which the benzyl ring of one molecule faces the ring of the subsequent one. Both mono- and dibenzyl templates show a high space-filling ability in AFI. Kinetic and thermodynamic factors that might affect the structure-directing activity of the molecules are examined.     

环聚炔苯和环聚炔吡啶组成的盘状液晶中的电荷转移

用电子转移的半经典模型在量子化学B3LYP/6-31G(d)水平(对单体)和B3LYP/STO-3G水平(对二聚物)对环聚炔苯和环聚炔吡啶组成的盘状液晶体系的电荷转移性质进行了研究. 盘状液晶体系的电荷转移速率主要依赖于重组能和电荷转移矩阵元, 重组能越小, 电荷转移矩阵元越大, 则电荷转移速率常数越大. 计算结果表明, 这些大环化合物比目前广泛研究和应用的苯并菲衍生物组成的液晶有较小的重组能, 所以有更好的电荷转移性质. 计算结果对有效地设计和合成高效的光导材料和载流子输送材料是有帮助的.     

Highly efficient methods for the preparation of shape-persistent macrocyclics

It has been about 25 years since Staab prepared a hexameric phenyl–ethynyl macrocycle by the statistical cyclization of the copper salt of m-iodo-phenylacetylene in 4.6% yield. Since that time, different methodologies have been investigated that allow not only the preparation of selectively functionalized structures, but also their formation in high yields. The repetitive formation of precursors followed by an intramolecular cyclization is only one approach to these structures. Alternatives include the use of covalently or noncovalently bound templates, as well as cyclization under thermodynamic control. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2685–2698, 1999     

ForceGen 3D structure and conformer generation: from small lead-like molecules to macrocyclic drugs

We introduce the ForceGen method for 3D structure generation and conformer elaboration of drug-like small molecules. ForceGen is novel, avoiding use of distance geometry, molecular templates, or simulation-oriented stochastic sampling. The method is primarily driven by the molecular force field, implemented using an extension of MMFF94s and a partial charge estimator based on electronegativity-equalization. The force field is coupled to algorithms for direct sampling of realistic physical movements made by small molecules. Results are presented on a standard benchmark from the Cambridge Crystallographic Database of 480 drug-like small molecules, including full structure generation from SMILES strings. Reproduction of protein-bound crystallographic ligand poses is demonstrated on four carefully curated data sets: the ConfGen Set (667 ligands), the PINC cross-docking benchmark (1062 ligands), a large set of macrocyclic ligands (182 total with typical ring sizes of 12–23 atoms), and a commonly used benchmark for evaluating macrocycle conformer generation (30 ligands total). Results compare favorably to alternative methods, and performance on macrocyclic compounds approaches that observed on non-macrocycles while yielding a roughly 100-fold speed improvement over alternative MD-based methods with comparable performance.     

Intramolecular co-operative hydrogen bond in calix[<Emphasis Type="Italic">n</Emphasis>]arenes (<Emphasis Type="Italic">n</Emphasis> = 4, 6, 8) bearing bulky substituents

Based on the Fourier transform IR spectroscopy together with the published NMR and X-ray data, it was shown that cyclic co-operative intramolecular hydrogen bond in calix[n]arene (n = 4, 6, 8) molecules is mainly responsible for their conformational state irrespective of the presence or absence of bulky substituents at the upper rim of the molecules. In accordance with the size of a macrocycle (n = 4, 6, 8), the stable conformation, secured by such a hydrogen bond, constitutes a cone, a pinched cone, and a pleated loop, respectively. The new, potentially competing system of hydrogen bonds in calix[6]arenes with 3-carboxymethyl-1-adamantyl substituents does not affect the conformational state of the macrocycle and its H-bonding. Six carboxy groups at the upper rim form in pairs three cyclic dimers, which does not disturb the hydrogen bonds of the hydroxy groups and the conformation of the macrocycle. In addition, the cavity of the molecule is considerably enlarged. The removal or rearrangement of the guest molecules in the solid calixarene by heating up to 180 °C only slightly affects the conformational state of macrocycles bearing bulky substituents, whereas in calixarenes devoid of such substituents, the similar procedure leads to somewhat of a distortion of the macrocycles (judging from the IR spectral indications of hydrogen bonding). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1062–1068, June, 2007.     

Effect of Substituents on the Supramolecular Structure and Stability of Crystals of Dialkylaminomethylated Calix[4]resorcinolarenes

The crystal and molecular structure of previously unknown dimethyl- and diethylaminomethylated calix[4]resorcinolarenes was determined by X-ray diffraction. The calixarene molecules occur in the crystal in the coneform, stabilized by the system of hydrogen bonds at the upper rim of the macrocycle. The crystal structure of the dimethylaminomethylated derivative includes 4.5 benzene molecules and an ethanol molecule per calixarene molecule. No solvent molecules are located inside the macrocycle cavity. In the structure of the diethylaminomethylated derivative there is one benzene molecule per calixarene molecule. The benzene molecule is located in the macrocycle cavity. The supramolecular structure of crystals is analyzed.     

Phenylacetylene macrocycles with two opposing bipyridine donor sites: syntheses, X-ray structure determinations, and Ru complexation

Reaction of the known macrocycle 1a, which contains two bipyridine units in opposing sides, with two equivalents of [Ru(bipy)2Cl2] furnishes the doubly exocyclically complexed macrocycle 8a in 55% yield. Synthesis of the shape-persistent macrocycle 1c by Hagihara-Sonogashira cross-coupling chemistry of suitably functionalized building blocks is reported. This macrocycle was also converted into a Ru complex (8c). X-ray analysis of single crystals of 1b and 1c shows a layered structure that contains "channels" filled with solvent molecules and parts of the flexible chains, with which the cycle is decorated for solubility reasons.