Metal–Ligand Cooperativity of the Calix[4]pyrrolato Aluminate: Triggerable C−C Bond Formation and Rate Control in Catalysis

Metal‐ligand cooperativity (MLC) had a remarkable impact on transition metal chemistry and catalysis. By use of the calix[4]pyrrolato aluminate, [ 1 ]^?, which features a square‐planar Al^III, we transfer this concept into the p‐block and fully elucidate its mechanisms by experiment and theory. Complementary to transition metal‐based MLC (aromatization upon substrate binding), substrate binding in [ 1 ]^? occurs by dearomatization of the ligand. The aluminate trapps carbonyls by the formation of C?C and Al?O bonds, but the products maintain full reversibility and outstanding dynamic exchange rates. Remarkably, the C?C bonds can be formed or cleaved by the addition or removal of lithium cations, permitting unprecedented control over the system's constitutional state. Moreover, the metal‐ligand cooperative substrate interaction allows to twist the kinetics of catalytic hydroboration reactions in a unique sense. Ultimately, this work describes the evolution of an anti‐van't Hoff/Le Bel species from their being as a structural curiosity to their application as a reagent and catalyst.     

N-硫脲基套索杯[4]冠醚与四硫脲基杯[4]芳烃的合成

控制反应物的物质的量比, 杯式对叔丁基杯[4]-1,3-二乙酸乙酯衍生物1与5或50倍二乙烯三胺反应, 分别得到杯[4]氮杂冠醚2和开链的氮杂杯[4]芳烃衍生物3. 化合物2和3进一步与异硫氰酸苯酯反应得到首例侧链含硫脲基的套索杯[4]氮杂冠醚4和含4个硫脲基的杯[4]芳烃衍生物5, 产率为92%和87%. 新化合物的结构与构象经元素分析、红外、质谱、核磁共振谱等表征证实.     

1,3-取代杯[4]芳烃三联吡啶配体的合成及其离子识别性能的研究

设计合成了1,3-取代杯[4]芳烃三联吡啶新型配体L1, 通过紫外吸收光谱的变化研究了配体L1对于Fe(II), Zn(II), Ni(II)等离子的识别作用.     

Synthesis of New Calix[4]arenes Functionalizated by Acetylhydrazide Groups

A series of new calix[4]phenols, calix[4]resorcinols and calix[4]pyrogallols with acetylhydrazide substitutes has been␣synthesized with high yields by hydrazinolysis of ester group containing calix[4]arenes. The synthesized calix[4]phenols adopt the cone conformation while the calix[4]resorcinol and calix[4]pyrogallol derivatives prefer the boat conformation. The amide fragment of the hydrazide groups predominantly exists in the trans-conformation. The binding ability of synthesized calix[4]arenes toward transition and alkali metals by solvent extraction has been investigated.     

Synthesis of （p-Formylphenyl）azo Calix[4]arenes

Five novel azo calix[4]arenes were reported. The p-aminobenzaldehyde was diazotized with sodium nitrite in aqueous hydrochloride solution. Mono-, bis-, tris- and tetrakis(p-formylphenyl)azo calix[4]arenes (including proximal and distal isomers) were obtained respectively by diazo-coupling in different molar ratio to calix[4]arene(1) under pH=7.5--8.5 at 0-5℃. All (p-formylphenyl)azo calix[4]arenes were characterized by ^1H NMR, ^13C NMR, IR, MS (ESIMS) spectroscopies and elemental analysis.     

Alkylations of Resorcarenes and Calix[4]pyrroles in Phase Transfer Catalytic Systems

Calixlnlarenesarecyclicoligomersmadeupofphenolsandformaldehyde.Thisversatileclassofcompoundshasbeenextensivelystudiedinthelastdecademainlyinordertoobtainnewcomplexingagentsbyappropriatefuntionalizationoftheparentmoleculel.ResorcarenesZandcall-c[4]pyrroles'aretwosubgroupmembersofthefamilyofcalixarensandalsoattractedincreasinginterests.Aspartofaprogrammeaimedatthesynthesisofneweasy-to-makecalixarenemolecules,wedecidedtoinvestigatethealkylationofsomecalixarensinPhaseTransferCatalysis(PTC)condi…     

Calix[4]pyrrole-based Crosslinked Polymer Networks for Highly Effective Iodine Adsorption from Water

A series of calix[4]pyrrole-based crosslinked polymer networks designed for iodine capture is reported. These materials were prepared by Sonogashira coupling of α,α,α,α-tetra(4-alkynylphenyl)calix[4]pyrrole with bishalide building blocks with different electronic properties and molecular sizes. Despite their low Brunauer–Emmett–Teller surface areas, iodine vapor adsorption capacities of up to 3.38 g g^?1 were seen, a finding ascribed to the presence of a large number of effective sorption sites including macrocyclic π-rich cavities, aryl units, and alkyne groups within the material. One particular system, C[4]P-BTP , was found to be highly effective at iodine capture from water (uptake capacity of 3.24 g g^?1 from a concentrated aqueous KI/I₂ solution at ambient temperature). Fast capture kinetics (k_obs=7.814 g g^?1 min^?1) were seen. Flow-through adsorption experiments revealed that C[4]P-BTP is able to remove 93.2 % of iodine from an aqueous source phase at a flow rate of 1 mL min^?1.     

Mono Halogen Substituted Calix[4]pyrroles: Fine-tuning the Anion Binding Properties of Calix[4]pyrrole

Abstract

Single halogen atom (i. e. I, Br, Cl and F) substituted calix[4]pyrroles, compounds 2, 3, 4 and 5, were synthesized. Studies of these systems reveal that replacement of a single β-pyrrolic hydrogen atom can increase the anion binding ability of calix[4]pyrroles for a variety of anions (e. g. Cl^?, Br^?, H₂PO₄ ^? and HSO^? ₄) relative to normal non-halogen substituted calix[4]pyrrole 1. In the case of chloride anion, the expected relative affinity sequence of 5 > 4 > 3 > 2 was observed. This was not found to be true for Br^?, H²PO^? ₄, and HSO^? ₄. Here, the chlorine substituted calix[4]pyrrole 4 was found to display a slightly higher affinity in the case of each anion than the fluorine-bearing derivative 5. This was rationalized in terms of intermolecular NH … F hydrogen bonding interactions being present in CD₂Cl₂ solutions of 5. Support for this latter conclusion came from concentration and temperature-dependent NMR spectroscopic studies.

A matched set of mono halogen substituted calix[4]pyrroles was used to study in detail, the extent to which halogen substituents may be used to fine-tune the anion binding properties of calix[4]pyrroles.     

杯[4]芳烃四丁醚的选择性硝化

硝化反应;杯[4]芳烃四丁醚的选择性硝化     

丙醛间苯二酚杯[4]芳烃烷基化衍生物的合成

以间苯二酚和丙醛为原料合成了丙醛杯[4]芳烃(1),1经不同的烷基化反应合成了新的丙醛杯[4]芳烃烷基化衍生物,其结构经1H NMR和IR表征。     

Syntheses of Chiral Calix [4] arene Derivatives Bearing Amino Acid Residue

The syntheses of chirai calix[4]arene derivatives bearing amino acid residue at the lower rim or upper rim by three different methods were reported.     

Catalytic Hydrogenation of meso‐Octamethylporphyrinogen (Calix[4]pyrrole)

Hydrogenation of meso‐octamethylporphyrinogen (calix[4]pyrrole) with a number of heterogeneous catalysts under different experimental conditions has been investigated. GC‐MS analyses of the reaction mixtures showed the formation of one to four products in low to moderate yields: three of them were diastereoisomers of the product derived from half‐hydrogenation of the substrate, and displayed alternating pyrrolidine and pyrrole rings, while the fourth was the all‐cis saturated product. An acidic medium was necessary to achieve hydrogenation. However, the use of too strongly acidic solvents or additives was detrimental to the stability of the substrate and/or the catalyst.     

基于杯[4]芳烃的手性识别*

手性杯芳烃是一类重要的主体化合物,在手性识别、对映体分离和不对称催化等方面有着广泛的用途。[4]芳烃引其稳定的构象和易于修饰的特点,成为研究最为广泛的杯芳烃分子,其中大量的文献报道了能够用于对映体识别和检测的手性[4]芳烃。在手性识别的研究中,荧光、紫外和核磁是3中最常见的研究方法,本文根据这3种方法进行分类,综述了近年来以杯[4]芳烃为分子骨架的手性受体的合成及其在手性识别中的应用。最后对手性[4]芳烃的发展前景作了展望。     

Effect of Calix[4]pyrrole as Addition Reagent on Anions Separation in Capillary Zone Electrophoresis (CZE)

Calixpyrroles, as new macrocyclic receptors, have gain increasing interest in host-guest chemistry. Pioneering work in this area by Sessler and co-workers have evidenced that calix[4]pyrroles are effective anion binding agents and have used for anion binding, sensing and new anion separation technologies1, 2. In this letter, we report that calix[4]pyrroles A, B and C3,4 (Scheme 1) can serve as additives in CZE for the separa- tion of halide ions. Scheme 1 A B C When analyzing anions with…     

Syntheses of Novel Chiral Calix[4]crown: Lariat Calix[4]-1,3-aza-crowns with Chiral Amino Acid Groups as Branched Chains

The first examples of lariat calix[4]-1,3-aza-crowns with chiral amino acid groups as branched chains (5a and 5b) were designed and synthesized via a 1 + 1 addition reaction of calix[4]-1,3-substituted benzaldehyde derivative (4) and amino acid hydrazide derivatives (3a and 3b) in yields of 70% and 75%, respectively. The preliminary extraction experiments suggested that hosts 5a and 5b possessed good complexation abilities for α-amino acids.      

新型杯[4]芳烃衍生物的合成

以对叔丁基杯[4]芳烃为起始原料,通过一步或两步取代反应合成了对叔丁基杯[4]芳烃的衍生物(1和2),其结构经FT-IR,^1H NMR,FAB-MS表征．     

杯[4]吡咯与含氧阴离子及其离子对弱相互作用的理论研究

在M06-2X/6-31+G(d,p)计算水平上,对杯[4]吡咯(CP)与3种不同构型的含氧阴离子OH-(C(v)、NO3-(D3h)、ClO4-(Td)形成的组装体系进行了理论研究。比较了各体系的构型、结合能、自然键轨道(NBO),利用多功能波函数软件Multiwfn对相互作用力等进行可视化分析。结果发现,无论主-客体的组装计量比是1∶1还是2∶1,阴离子的构型直接影响组装体系的构型。阴离子空间构型越大、整体电负性越强,越倾向于2∶1复合体系。考虑到杯[4]吡咯是典型的离子对受体,本文还研究了主体与NH4+-阴离子的离子对体系的相互作用。在离子对的组装过程中,由于阴、阳离子间的作用占据了主导,从而减弱了阴离子与主体间氢键作用,无论阴离子构型如何,主体与离子对的组装都倾向于1∶1的作用体系。本文结果对深入理解杯吡咯类受体的离子识别作用本质,拓展该类超分子主体的应用范围具有重要的理论意义。     

One-dimensional Inclusion Polymers of Calix[4]arene Monomethoxycarboxylic Acid

X-ray crystal structures of the inclusion complexes of calix[4]arene monomethoxycarboxylic acid 1 （C30H2606） with acetontrile and acetone are reported. The crystal of C30H26O6·CH3CN is of monoclinic, space group P2 1/c with a = 11.691（5）, b = 13.753（5）, c = 17.072（7）A, β = 100.104（7）°, C32H29NO6, Mr = 523.56, V = 2702.4（18）A^3, Z = 4, De= 1.287 g/cm^3, μ（MoKα） = 0.089 mm^-1, T = 293（2） K, 5570 independent reflections with 3220 observed ones （1 〉 2σ（I））, R = 0.0521 and wR = 0.1132 with GOF = 1.042 （R = 0.1055 and wR = 0.1350 for all data）. The data for C30H26O6·CH3COCH3： monoclinic, space group P2 1/c, α = 12.366（4）, b = 12.119（4）, c = 18.796（6） A, β = 90.871（6）°, C33H32O7, Mr = 540.59, V = 2816.6（16）A^3, Z = 4, Dc = 1.275 g/cm^3, μ（MoKα） = 0.089 mm^-1, T = 293（2） K, 5783 independent reflections including 2580 observed ones （I 〉 2σ（I））, R = 0.0555 and wR = 0.1424 with GOF= 0.975 （R = 0.1601 and wR = 0.1884 for all data）. Their architectures exhibit one-dimensional inclusion polymers which are mediated head-to-tail by the guests.     

一锅法合成含两种桥联链的杯[4]双冠醚和双杯[4]冠醚

报道了"一锅法"合成含两种桥联链的新型杯[4]双冠醚和双杯[4]冠醚.杯[4]芳烃先与N,N’-乙撑基-二(2-氯乙酰胺)发生"1+1"缩合反应,然后直接加入三甘醇双对甲苯磺酸酯继续进行"2+2"缩合反应,合成了含两种桥联链的新型双杯[4]冠醚4.按照相似程序,杯[4]芳烃先后与N,N’-乙撑基-二(2-氯乙酰胺)、溴乙酸乙酯和二乙烯三胺反应,得到含两种桥联链的新型杯[4]双冠醚5.化合物5进一步与异硫氰酸苯酯反应合成带硫脲支链的杯[4]双冠醚6.所有新化合物的结构与构象经元素分析、质谱、核磁共振谱等表征证实.     

新型杯[4]芳烃酰肼基羰基羧酸衍生物的合成

杯[4]芳烃经醚化引入酯基后再经水合肼肼解,进一步与丁二酸酐或顺丁烯二酸酐氨解开环合成了两个新型的杯[4]芳烃酰肼基羰基羧酸衍生物,产率85％和83％,其结构经1H NMR,IR和ESI-MS表征.