环番的合成及其应用的研究进展

环番作为一种人工合成受体,具有多个活性位点和一定的空腔尺寸等诸多特性,因而具有分子识别、光学性质、催化活性和药物活性等诸多性质,在许多领域有着广泛的应用前景。总结了近年来环番的合成方法及各自的优缺点,并介绍了其性质、应用等方面的研究进展。     

瓜环试剂的发展及应用研究

瓜环是超分子领域中的一类备受关注的新兴大环化合物,但由于其溶解度小、活性基团少、难以衍生化等因素,一定程度上限制其发展和广泛应用.简要介绍了瓜环的发展历程,全面介绍了常见瓜环化合物的合成、分离与表征,进一步介绍了各种衍生化瓜环,重点介绍了各种瓜环在分子包结与识别和分子催化等方面的应用,讨论了瓜环类试剂发展中存在的问题及...     

季戊四醇的超分子化学

介绍季戊四醇的超分子化学,包括超分子网状结构、螺环冠醚、非常规液晶、富勒烯衍生物、固相光催化反应、Janus树枝状分子等等。     

瓜环化合物的超分子自组装研究新进展

简要介绍了瓜环化合物的结构特征、性质及应用。详细综述了：①瓜环化合物的主客体配位作用及其超分子结构;②瓜环与碱金属和碱土金属的配位组装及超分子结构;③六元瓜环与过渡金属离子及镧系离子形成的超分子自组装结构。     

七元瓜环与N-戊基-4-吡咯烷基吡啶溴化物的自组装

设计合成了客体分子N-戊基-4-吡咯烷基吡啶吡啶衍生物,利用核磁共振光谱和紫外-可见吸收光谱法考察了主体七元瓜环(Q[7])与客体N-戊基-4-吡咯烷基吡啶吡啶溴化物(G)的自组装模式。结果表明这两种测试方法相互佐证,在水溶液中,Q[7]包结G的吡啶环、吡咯环以及部分烷基链部分,形成1∶1的包结配合物,这一特性不仅可用于构筑新颖奇特的超分子体系,而且为分子开关的制备研究提供了有用的信息。     

超分子化合物的合成与识别研究的新进展

简要介绍了超分子化学的产生发展及应用,重点综述了：①新型大环超分子化合物的合成及对阴离子的识别作用;②超分子受体的合成及对金属离子的识别作用;③新型二茂铁双内酯环蕃超分子受体的合成及选择性识别作用。并对超分子化学的发展进行了展望。     

化学领域的前沿──超分子化学

超分子化学是一个蓬勃发展的化学新领域，本文综述了超分子化学发展概况，重点介绍了分子识别、分子自组装、超分子材料、超分子器件及超分子催化方面的新成果，简明阐述了超分子体系形成的理论基础，同时引入了分子光子学、分子电子学、分子离子学、超分子科学等前沿学科。     

基于大环化合物主-客体作用的超分子聚合物凝胶材料研究进展

综述了近年来冠醚、环糊精、葫芦脲和柱芳烃等大环化合物的衍生物通过主-客体作用形成的超分子聚合物凝胶材料的研究情况。指出了该材料对温度、酸碱度、溶剂和客体分子等外界环境刺激敏感,在智能响应性方面表现出了优异的性质。对超分子聚合物凝胶材料未来的研究方向进行了展望。     

基于大环化合物主-客体作用的超分子聚合物凝胶材料研究进展

综述了近年来冠醚、环糊精、葫芦脲和柱芳烃等大环化合物的衍生物通过主-客体作用形成的超分子聚合物凝胶材料的研究情况。指出了该材料对温度、酸碱度、溶剂和客体分子等外界环境刺激敏感,在智能响应性方面表现出了优异的性质。对超分子聚合物凝胶材料未来的研究方向进行了展望。     

含单种杂原子的桥联杯芳烃的合成研究进展

综述了含单种杂原子的桥联杯芳烃的合成研究进展。目前合成的大多数的杯芳烃都是碳桥联的,除了碳,如硼、硅、锗、锡、氮、磷、氧、硫、硒原子都可以作为桥联原子建构杯芳烃,其中硅、氮、氧、硫桥杯芳烃报道文献较多,介绍了含单种杂原子的桥联杯芳烃的合成条件及其应用。     

超分子大环配体环蕃化合物的合成应用及分子识别

简要介绍了环蕃的结构特征、性质及应用,详细综述了:①新型超分子大环配体环蕃的合成及应用;②新型环蕃的合成及选择性识别作用;③新型手性环蕃的合成及应用。     

Stereocontrol in cyclophane synthesis: a photochemical method to overlap aromatic rings

To overlap aromatic rings in cyclophanes, the inter- and intramolecular [2 + 2] photocycloaddition of vinylarenes has been developed. It gives cyclophanes, naphthalenophanes, phenanthrenophanes, thiophenophanes, and carbazolophanes in reasonable to excellent yields. The structures and properties of cyclophanes obtained are reviewed; especially the excimer emission of phenanthrenophanes, naphthalenophanes, and carbazolophanes stressed that many intriguing cyclophanes can be obtained through the fine molecular design of precursors.     

1,2,3-Triazolophanes—Cyclophanes with an Array of Molecular Structures and Supramolecular Architectures

1,2,3-Triazolophanes are a class of cyclophanes that has attracted enormous attention in recent times. With the advent of the intramolecular copper-mediated alkyne azide cycloaddition (CuAAC) reaction 1,2,3-triazolophanes of various molecular structure and supramolecular architecture have been synthesized. 1,2,3-Triazolophanes find a variety of applications as molecular hosts, ion sensors, peptidomimics, and supramolecular building blocks, among others.     

Etude electrochimique du cation argent en presence de |2.2.2| paracyclophane (π-prismand) et de molecules apparentees

The equilibrium constants K corresponding to the formation of complexes of cyclophanes with Ag⁺ cation in nitromethane and methanol are calculated from voltammetric and potentiometric measurements ¦2.2.2¦paracyclophane is found to be the most powerful complexant with K = 25,000 and 3000 in nitromethane and methanol respectively. For the other ligands, the constant K is about 100 times lower.     

Concave π-prismand hydrocarbon [2.2.2]cyclophanes and their crystalline Ag-triflate complexes

New small concave hydrocarbon cyclophanes were prepared via the well-known HD-2SO₂-method. The cyclophanes obtained are isomers of the very well-known [2.2.2]p,p,p-cyclophane, C₂₄H₂₄, a π-prismand efficiently complexing Ag⁺-ion. X-ray crystal structure determinations showed the bis-sulfide 7 (1,10-dithia[3.3.2]m,p,p-cyclophane) to be helically chiral and that the conformation of the parent hydrocarbon cyclophane 13 ([2.2.2]m,p,p-cyclophane) does not change dramatically upon complexation with the Ag⁺-ion. The 16- and 17-membered [2.2.2]m,m,p- and [2.2.2]m,p,p-cyclophane ( 15 and 16 ) also act as π-prismands and form surprisingly similar crystalline 1:1 Ag-triflate complexes (π-prismates) as the well-known 18-membered p,p,p-isomer proved by the X-ray structure analysis.     

Olefination Reactions in the Synthesis of Cyclophanes

A survey of olefination reactions that have been used in the synthesis of cyclophanes is presented. This covers the Ramberg–Bäcklund reaction, the Wittig and related reactions, the McMurry and related reactions, ring-closing metathesis (alkenes, alkynes and ene-ynes), aldol condensations and Siegrist reactions, as well as miscellaneous reactions. The McMurry reaction and ring-closing metathesis have enjoyed the greatest popularity in recent years, but they are typically used for complementary purposes. In virtually all cases, the McMurry reaction is used to install a two-carbon (1,2-ethenylene) bridge, whereas ring-closing metathesis is used to construct bridges that are at least four-membered, but usually considerably longer. Some well-known olefinations have seen little or no use in the field of cyclophane chemistry.     

From [10]Paracyclophane to Ferrocenophanones: The Search for Molecular Machines and Bio-Organometallic Anticancer Drugs

A partial quenching of the NMR ring current in [10]paracyclophane-chromium tricarbonyl prompted a study of other metal–arene π complexes, several of which exhibited restricted intramolecular motion relevant to their potential use in molecular machines. An attempted Diels–Alder reaction of 9-phenylethynyl-9H-fluorene with tetracyclone instead yielded a novel tetracene by isomerization of the alkyne to the corresponding allene, and then via a series of allene dimers which are classifiable as cyclophanes. (Subsequently, the first organometallic molecular brake was prepared, whereby migration of a metal carbonyl tripod over an indenyl framework blocked the rotation of a triptycene paddlewheel.) Cyclophanes have now found applicability in the field of bio-organometallic chemistry; the activity of tamoxifen, the first line treatment for hormone-dependent breast cancers, is markedly enhanced when the structure is modified by incorporation of a ferrocenophane moiety. Finally, we relate the story of how the first cyclophane, [1.1.1]orthocyclophane, was actually prepared by Cannizzaro in 1854, but was only recognized as such more than 150 years later.     

Two Syntheses of [2.2.2] (1,2,3)Cyclophane

Two syntheses are presented for [2.2.2] (1,2,3)cyclophane (7), the remaining member of the symmetrical [2_n]cyclophanes whose preparation has not previously been described. The first method involved the dimerization of 2,6-bis (4′, 4′-dimethyl-2′-oxazolinyl)toluene ( 1 ) to give 2 which, on hydrolysis, produced the tetracarboxylic acid 3 . Conversion of 3 , via the acid chloride ( 4 ), to the tetraol 5 , followed by treatment with phosphorus tribromide yielded the tetrabromide 6 . The overall scheme was then completed by reaction of 6 with phenyllithium to give [2.2.2] (1,2,3) cyclophane ( 7 ). An alternate, more convenient, method began with the pyrolysis of 2,6-bis (chloromethyl)toluene ( 8 ) to give 3-chloromethylbenzocyclobutene ( 9 ). Formation of the Grignard of 9, followed by reaction with ferric chloride, yielded the dimer 10 . Pyrolysis of 10 then gave [2.2.2] (1,2,3)cyclophane (7).