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Search for "cage compounds" in Full Text gives 12 result(s) in Beilstein Journal of Organic Chemistry.
Mechanistic studies of the solvolysis of alkanesulfonyl and arenesulfonyl halides
- Malcolm J. D’Souza and
- Dennis N. Kevill
Beilstein J. Org. Chem. 2022, 18, 120–132, doi:10.3762/bjoc.18.13
- some other pure or mixed solvent. The sensitivity value m is set at unity for the standard solvolysis and then for some other solvent the solvent ionizing power (Y) will be given by log (k/ko). Subsequently, with the ready availability of cage compounds (1-adamantyl and 2-adamantyl with a leaving group
Graphical Abstract
Scheme 1: Organic reactions where the breaking of a C–X bond involves the formation of a high energy ion-pair...
Scheme 2: The chemical structures for the 1-adamantyl substrate, 2-adamantyl substrate, and the S-methyldiben...
Figure 1: The SN2 reaction plot of log (k/ko) vs (1.26 NT + 0.65 YCl) for the solvolyses of benzesulfonyl chl...
Figure 2: The SN2 reaction plot of log (k/ko) vs (1.35 NT + 0.70 YCl) for the solvolyses of 2-thiophenesulfon...
A heterobimetallic tetrahedron from a linear platinum(II)-bis(acetylide) metalloligand
- Matthias Hardy,
- Marianne Engeser and
- Arne Lützen
Beilstein J. Org. Chem. 2020, 16, 2701–2708, doi:10.3762/bjoc.16.220
- diastereomers. The new complexes were characterized by NMR and UV–vis spectroscopy and ESI mass spectrometry. Using GFN2-xTB we generated energy-minimized models of the diastereomers of this cage that further corroborated the results from analytical findings. Keywords: cage compounds; heterobimetallic
Graphical Abstract
Scheme 1: Stepwise assembly of the heterobimetallic tetrahedron 4, starting from 4-ethynylaniline (1) and tra...
Figure 1: ESI(+) mass spectrum of heterobimetallic complex 4. The top inset shows the experimentally observed...
Figure 2: UV–vis spectrum of heterobimetallic complex 4 (1150 µM in acetonitrile at 295 K, 0.01 mm cuvette).
Figure 3: Schematic representation of symmetry-considerations concerning possible diastereomeric tetrahedra. ...
Figure 4: Detailed excerpt of the 31P NMR spectrum of 4 (202 MHz, acetonitrile-d3, 298 K).
Figure 5: 1H NMR and DOSY spectrum of heterobimetallic assembly 4 (500 MHz, acetonitilre-d3, 298 K).
Figure 6: GFN2-xTB minimized gas phase models of the cationic units of all possible diastereomers of 4. Color...
A new method for the synthesis of diamantane by hydroisomerization of binor-S on treatment with sulfuric acid
- Rishat I. Aminov and
- Ravil I. Khusnutdinov
Beilstein J. Org. Chem. 2020, 16, 2534–2539, doi:10.3762/bjoc.16.205
- reaction stops after the hydrogenation step giving endo-endo-pentacyclo[7.3.1.12,5.18,10.03,7]tetradecane in 68% yield with excellent selectivity (100%). Keywords: binor-S; diamantane; hydroisomerization; sulfuric acid; tetrahydrobinor-S; Introduction Among the highly diverse polycyclic and cage
- compounds, an important place is occupied by diamond-like compounds called diamondoids, whose lower representatives belong to the homologous series C4n+6H4n+12. Owing to the rigid structure, diamondoids typically have high thermal stability and high reactivity compared with aliphatic and alicyclic saturated
Graphical Abstract
Scheme 1: Isomerization of 3а–с to diamantane (1). Reaction conditions: (a) CoBr2·2PPh3–BF3·OEt2, 110 °C, 12 ...
Scheme 2: Isomerization of binor-S (2) to diamantane (1).
Scheme 3: Selective synthesis of tetrahydrobinor-S (3c) from binor-S (2).
Scheme 4: Isomerization of binor-S (2) to hydrocarbons 4а and b.
Host–guest interaction of cucurbit[8]uril with oroxin A and its effect on the properties of oroxin A
- Zhishu Zeng,
- Jun Xie,
- Guangyan Luo,
- Zhu Tao and
- Qianjun Zhang
Beilstein J. Org. Chem. 2020, 16, 2332–2337, doi:10.3762/bjoc.16.194
- the inclusion compound with Q[8]. Keywords: cucurbit[8]uril; host–guest interaction; inclusion complex; oroxin A; properties; Introduction Cucurbit[n]urils (Q[n]s) are a family of macrocyclic cage compounds synthesized by the condensation of glycoluril and formaldehyde in a strong acidic solution [1
Graphical Abstract
Figure 1: The molecular structure of OA (A) and Q[8] (B).
Figure 2: 1H NMR titration of OA with Q[8] were performed in D2O containing 10% DMSO by volume, OA (500 μmol·L...
Figure 3: (A) The UV–vis absorption spectra recorded for OA in the presence of Q[8] (c(Q[8]), labeled a–k: 0,...
Figure 4: IR spectra recorded for (a) Q[8], (b) OA, (c) a physical mixture of Q[8] and OA, and (d) the OA@Q[8...
Figure 5: The possible interaction mode for OA@Q[8].
Figure 6: The phase-solubility graph obtained for OA in a Q[8] aqueous solution at λ = 275 nm.
Figure 7: The clearance rate curve of ABTS+• upon increasing the concentration of OA and the OA@Q[8] inclusio...
Figure 8: The release curves of OA and OA@Q[8].
Mechanochemistry of supramolecules
- Anima Bose and
- Prasenjit Mal
Beilstein J. Org. Chem. 2019, 15, 881–900, doi:10.3762/bjoc.15.86
- cages under high-speed vibration milling (HSVM) conditions. The condensation of pentaerythritol and triboronic acid at 58 Hz for 40 min led to the formation of cage structure 22 (Figure 11) with nearly 96% yield [64]. The authors also reported that the cage compounds such as 22 had high thermal
Graphical Abstract
Figure 1: A generalized overview of coordination-driven self-assembly.
Figure 2: Examples of self-assembly or self-sorting and subsequent substitution.
Figure 3: Synthesis of salen-type ligand followed by metal-complex formation in the same pot [55].
Figure 4: Otera’s solvent-free approach by which the formation of self-assembled supramolecules could be acce...
Figure 5: Synthesis of a Pd-based metalla-supramolecular assembly through mechanochemical activation for C–H-...
Figure 6: a) Schematic representation for the construction of a [2]rotaxane. b) Chiu’s ball-milling approach ...
Figure 7: Mechanochemical synthesis of the smallest [2]rotaxane.
Figure 8: Solvent-free mechanochemical synthesis of pillar[5]arene-containing [2]rotaxanes [61].
Figure 9: Mechanochemical liquid-assisted one-pot two-step synthesis of [2]rotaxanes under high-speed vibrati...
Figure 10: Mechanochemical (ball-milling) synthesis of molecular sphere-like nanostructures [63].
Figure 11: High-speed vibration milling (HSVM) synthesis of boronic ester cages of type 22 [64].
Figure 12: Mechanochemical synthesis of borasiloxane-based macrocycles.
Figure 13: Mechanochemical synthesis of 2-dimensional aromatic polyamides.
Figure 14: Nitschke’s tetrahedral Fe(II) cage 25.
Figure 15: Mechanochemical one-pot synthesis of the 22-component [Fe4(AD2)6]4− 26, 11-component [Fe2(BD2)3]2− ...
Figure 16: a) Subcomponent synthesis of catalyst and reagent and b) followed by multicomponent reaction for sy...
Figure 17: A dynamic combinatorial library (DCL) could be self-sorted to two distinct products.
Figure 18: Mechanochemical synthesis of dynamic covalent systems via thermodynamic control.
Figure 19: Preferential formation of hexamer 33 under mechanochemical shaking via non-covalent interactions of...
Figure 20: Anion templated mechanochemical synthesis of macrocycles cycHC[n] by validating the concept of dyna...
Figure 21: Hydrogen-bond-assisted [2 + 2]-cycloaddition reaction through solid-state grinding. Hydrogen-bond d...
Figure 22: Formation of the cage and encapsulation of [2.2]paracyclophane guest molecule in the cage was done ...
Figure 23: Formation of the 1:1 complex C60–tert-butylcalix[4]azulene through mortar and pestle grinding of th...
Figure 24: Formation of a 2:2 complex between the supramolecular catalyst and the reagent in the transition st...
Figure 25: Halogen-bonded co-crystals via a) I···P, b) I···As, and c) I···Sb bonds [112].
Figure 26: Transformation of contact-explosive primary amines and iodine(III) into a successful chemical react...
Figure 27: Undirected C–H functionalization by using the acidic hydrogen to control basicity of the amines [114]. a...
Tetrathiafulvalene – a redox-switchable building block to control motion in mechanically interlocked molecules
- Hendrik V. Schröder and
- Christoph A. Schalley
Beilstein J. Org. Chem. 2018, 14, 2163–2185, doi:10.3762/bjoc.14.190
- topologically complex TTF catenanes and cage compounds [52][74][102][103][104]. 6.1. Stimuli-responsive circumrotation The TTF-based catenane 26 allows implementing a stimuli-responsive circumrotation motion (Figure 24) [105]. Similar to the corresponding donor–acceptor rotaxanes, the macrocycle preferentially
Graphical Abstract
Figure 1: The two one-electron oxidation reactions of tetrathiafulvalene (TTF, 1) and the corresponding prope...
Figure 2: UV–vis spectra and photographs of TTF 2 in its three stable oxidation states (black line = 2, orang...
Figure 3: Structure and conformations of two TTF dimers in solution, the mixed-valence and the radical-cation...
Figure 4: (a) The isomerism problem of TTF. (b)–(d) Major synthetic breakthroughs for the construction of TTF...
Figure 5: (a) Host–guest equilibrium between π-electron-poor cyclophane 3 and different TTFs with their corre...
Figure 6: TTF complexes with different host molecules.
Figure 7: Stable TTF (a) radical-cation and (b) mixed-valence dimers in confined molecular spaces.
Figure 8: A “three-pole supramolecular switch”: Controlled by its oxidation state, TTF (1) jumps back and for...
Figure 9: Redox-controlled closing and opening motion of the artificial molecular lasso 12.
Figure 10: Graphical illustration how a non-degenerate TTF-based shuttle works under electrochemical operation....
Figure 11: The first TTF-based rotaxane 13.
Figure 12: A redox-switchable bistable molecular shuttle 14.
Figure 13: The redox-switchable cyclodextrin-based rotaxane 15.
Figure 14: The redox-switchable non-ionic rotaxane 16 with a pyromellitic diimide macrocycle.
Figure 15: The redox-switchable TTF rotaxane 17 based on a crown/ammonium binding motif.
Figure 16: Structure and operation of the electro- and photochemically switchable rotaxane 18 which acts as po...
Figure 17: (a) The redox-switchable rotaxane 19 with a donor–acceptor pair which is stable in five different s...
Figure 18: Schematic representation of a molecular electronic memory based on a bistable TTF-based rotaxane. (...
Figure 19: Schematic representation of bending motion of a microcantilever beam with gold surface induced by o...
Figure 20: TTF-dimer interactions in a redox-switchable tripodal [4]rotaxane 22.
Figure 21: (a) A molecular friction clutch 23 which can be operated by electrochemical stimuli. (b) Schematic ...
Figure 22: Fusion between rotaxane and catenane: a [3]rotacatenane 24 which can stabilize TTF dimers.
Figure 23: The first TTF-based catenane 25.
Figure 24: Electrochemically controlled circumrotation of the bistable catenane 26.
Figure 25: A tristable switch based on the redox-active [2]catenane 27 with three different stations.
Figure 26: Structure of catenane-functionalized MOF NU-1000 [108] with structural representation of subcomponents. ...
Figure 27: (a) [3]Catenanes 29 and 30 which can stabilize mixed-valence or radical-cation dimers of TTF. (b) S...
Glycoscience@Synchrotron: Synchrotron radiation applied to structural glycoscience
- Serge Pérez and
- Daniele de Sanctis
Beilstein J. Org. Chem. 2017, 13, 1145–1167, doi:10.3762/bjoc.13.114
- shorter than the time scale of substrate diffusion in the crystals. For example, when UDP-GalNAc was soaked for 24 minutes, experiments resulted in structures with UDP-GalNAc in several conformations that are difficult to interpret. The “freeze-trigger” route was started using a series of cage compounds
Graphical Abstract
Figure 1: Complementarity of synchrotron radiation and neutron sources to investigate the structure of matter....
Figure 2: A representation of a synchrotron storage ring, including linear accelerator, booster and two beaml...
Figure 3: Schematic representation of a sector of a storage ring. Bending magnets and insertion devices are a...
Figure 4: Structural features of the resin glycoside tricolorin A. (a) Extracted from the Mexican variety of ...
Figure 5: Powder diffractogram measured on a synthetic pentasaccharide from heparin, at ESRF beamline ID31, λ...
Figure 6: Three dimensional ribbon representation of a heavily N-glycosylated Aspergilllus sp. Family GH3 β-D...
Figure 7: Histogram of the number of deposited crystal structures of glycan-binding proteins deposited over t...
Figure 8: Ribbon diagram representations of prototypical members of the GT-A and GT-B super-family fold, resp...
Figure 9: Representation of the FUT1 structure determined in complex with the acceptor (carbon atoms in green...
Figure 10: Representation of the seven folds most commonly found in glycoside hydrolases. From the classificat...
Figure 11: The multivalent carbohydrate binding features of lectins from X-ray structures. (a) Monovalent. E-s...
Figure 12: Three-dimensional depiction of the ternary complex formed by a heparin mimetic in interaction with ...
Figure 13: 3D representation of different sugar transporter structures: (left to right, top to down) lactose p...
Figure 14: Kinetic crystallography. Protein crystals are soaked with the cage compound (Step 1) followed by fl...
Figure 15: Reconstruction of the full three-dimensional structure of the soluble lectin (BC2L-C) from the oppo...
Figure 16: Characterization by synchrotron X-ray reflectometry of the transverse structures of a model membran...
Figure 17: Complementary use of X-ray synchrotron and neutron fiber diffraction to unravel the three-dimension...
Figure 18: Scanning electron micrograph of high-quality micrometer-sized A-amylose microcrystals grown from sh...
Figure 19: Cartography of distribution and orientation of cellulose in wood using a 3 µm X-ray beam. The scann...
Figure 20: Structural micro-diffraction scanning of a starch granule from Phajus grandifolius with dimensions ...
Interactions between shape-persistent macromolecules as probed by AFM
- Johanna Blass,
- Jessica Brunke,
- Franziska Emmerich,
- Cédric Przybylski,
- Vasil M. Garamus,
- Artem Feoktystov,
- Roland Bennewitz,
- Gerhard Wenz and
- Marcel Albrecht
Beilstein J. Org. Chem. 2017, 13, 938–951, doi:10.3762/bjoc.13.95
- ; shape persistent polymers; Introduction Shape-persistence is an important key feature in self-organisation strategies of supramolecular building blocks resulting in high structural perfection of the obtained molecular assemblies [1], such as shape persistent macrocycles, cage compounds or rotaxanes [2
Graphical Abstract
Figure 1: Interaction of a shape-persistent CD polymer with ditopic guests.
Figure 2: Schematic representation of tip and surface modifications realized in this study (bottom). Blue lin...
Scheme 1: Synthesis of the CD polymer. a) conc. HNO3, reflux, 6 d; b) tert-butanol, cat. H2SO4, MgSO4, CH2Cl2...
Figure 3: Absorption spectra of monomer 7 (solid red line) and polymer 8 (solid blue line) in water. Emission...
Figure 4: Positive linear MALDI–TOF spectrum of polymer 8 using HABA/TMG2 matrix.
Figure 5: SANS data for polymer 8 and fit by cylindrical model (solid line).
Scheme 2: Ditopic and monotopic guest molecules.
Figure 6: Solubility of polymer 8 in the presence of ditopic connector 9 (black graph) and 1-aminoadamantane ...
Scheme 3: Synthesis of amino functionalized polymer 12.
Figure 7: Characteristic force curves recorded during retraction of the AFM tip from the surface. Four functi...
Figure 8: Graphical summary of experimental results for the four configurations of CD attachment introduced i...
Figure 9: (a) Detail of the end of a force curve for a polymer-functionalized tip retracted from a polymer-fu...
Figure 10: Characteristic result of a friction experiment for a polymer-functionalized tip sliding on a surfac...
Supramolecular frameworks based on [60]fullerene hexakisadducts
- Andreas Kraft,
- Johannes Stangl,
- Ana-Maria Krause,
- Klaus Müller-Buschbaum and
- Florian Beuerle
Beilstein J. Org. Chem. 2017, 13, 1–9, doi:10.3762/bjoc.13.1
- frameworks (MOFs) [17][18], covalent organic frameworks (COFs) [19][20] or covalent organic cage compounds [21][22][23][24][25][26][27][28] as the most prominent examples for such artificial porous materials. Purely organic systems such as COFs usually benefit from very low densities, high thermal
Graphical Abstract
Figure 1: Icosahedral arrangement of functional addends for [60]fullerene hexakisadducts with dodecaacids C2 ...
Figure 2: a) Small cavities within the octahedral sites of HFF-1 filled with one CH2Cl2 molecule [57]; b) isolate...
Scheme 1: Synthesis of [60]fullerene dodecaacid C4.
Figure 3: Face centered cubic arrangement of [60]fullerene dodecaacids for frameworks a) HFF-1 [57], b) HFF-2 and...
Figure 4: Hydrogen bonding network for HFF-3 (left, hydrogen bonds yellow) and porous channels along the c ax...
Figure 5: Interpenetration of two distinct hydrogen bonding networks for HFF-3: a) side view indicating the s...
Bridgehead vicinal diallylation of norbornene derivatives and extension to propellane derivatives via ring-closing metathesis
- Sambasivarao Kotha and
- Rama Gunta
Beilstein J. Org. Chem. 2016, 12, 1877–1883, doi:10.3762/bjoc.12.177
- dienophile [6][7][8]. Cage compounds with interesting applications have been assembled by a cyclization reaction starting with suitably functionalized norbornene derivatives [9][10][11]. Moreover, the norbornene unit induces a hairpin-like architecture when it is incorporated into a peptide chain. This
Graphical Abstract
Figure 1: Retrosynthetic approach to propellane derivatives.
Scheme 1: Synthesis of the propellane derivative 1a via RCM.
Scheme 2: Garratts work on alkylation of norbornene with retention of configuration.
Figure 2: The molecular structure of 1a, with displacement ellipsoids drawn at the 50% probability level.
Scheme 3: Control experiment carried out to probe the configuration of 2a.
Figure 3: Crystal structure of compound 15 showing 50% displacement ellipsoids.
Scheme 4: RCM of the compound 2aa'.
Scheme 5: RCM approach to the propellane derivative 1b.
Figure 4: The molecular structures of the compounds 2b (left) and 1b (right) showing 30% displacement ellipso...
Scheme 6: Construction of the propellane derivative 1bb' using RCM.
Spiro annulation of cage polycycles via Grignard reaction and ring-closing metathesis as key steps
- Sambasivarao Kotha,
- Mohammad Saifuddin,
- Rashid Ali and
- Gaddamedi Sreevani
Beilstein J. Org. Chem. 2015, 11, 1367–1372, doi:10.3762/bjoc.11.147
- ) reaction as a key step is described. The structures of three new cage compounds 7, 12 and 18 were confirmed by single crystal X-ray diffraction studies. Keywords: cage molecules; Diels–Alder reaction; Grignard reaction; ring-closing metathesis; spirocycles; Introduction Design and synthesis of
- antiviral properties [22]. Although, several methods are available for the construction of cage compounds [7][23][24][25][26][27][28][29][30][31][32][33], the synthesis of symmetrical spiro-cage molecule 7 seems to be a synthetic challenge due to the proximity of the two carbonyl groups in dione 10 which
- screened to optimize the yields. Finally, we found that the Grubbs’ first generation catalyst (G-I) in refluxing toluene gave the desired RCM product 7 in 85% yield. Along similar lines, the triallyl compound 16 gave the RCM product 17 in 66% yield (Scheme 4). The structures of the annulated cage compounds
Graphical Abstract
Figure 1: Structures of diverse biologically as well as theoretically interesting molecules.
Figure 2: Retrosynthetic analysis of bis-spiro-pyrano cage compound 7.
Scheme 1: Synthesis of hexacyclic cage dione 10.
Scheme 2: Synthesis of tetrahydrofuran-based cage compounds 12 and 13.
Figure 3: (a)Optimized structure of 12, (b) optimized structure of 13.
Scheme 3: Synthesis di-allyl cage compound 11.
Scheme 4: Synthesis of spiro-pyrano cage molecules 7 and 17.
Figure 4: (a) Optimized structure of 18, (b) optimized structure of 7.
Scheme 5: Synthesis of octacyclic cage compound 18 via intramolecular DA reaction.
Scheme 6: Attempted synthesis to cage compound 20.
Selected synthetic strategies to cyclophanes
- Sambasivarao Kotha,
- Mukesh E. Shirbhate and
- Gopalkrushna T. Waghule
Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142
- tripodal cage compounds (e.g., 280) by using a [2 + 2 + 2] cycloaddition reaction of branched triynes (Scheme 47). The best results for a cycloaddition were observed when triyne 279 was added dropwise over a period of 10 min to a solution of a chiral catalyst at elevated temperature (120 °C). Also, highly
Graphical Abstract
Figure 1: General representation of cyclophanes.
Figure 2: cyclophanes one or more with heteroatom.
Figure 3: Metathesis catalysts 12–17 and C–C coupling catalyst 18.
Figure 4: Natural products containing the cyclophane skeleton.
Figure 5: Turriane family of natural products.
Scheme 1: Synthesis of [3]ferrocenophanes through Mannich reaction. Reagents and conditions: (i) excess HNMe2...
Scheme 2: Synthesis of cyclophanes through Michael addition. Reagents and conditions: (i) xylylene dibromide,...
Scheme 3: Synthesis of normuscopyridine analogue 37 through an oxymercuration–oxidation strategy. Reagents an...
Scheme 4: Synthesis of tribenzocyclotriyne 39 through Castro–Stephens coupling reaction. Reagents and conditi...
Scheme 5: Synthesis of cyclophane 43 through Glaser–Eglinton coupling. Reagents and conditions: (i) 9,10-bis(...
Scheme 6: Synthesis of the macrocyclic C-glycosyl cyclophane through Glaser coupling. Reagents and conditions...
Scheme 7: Synthesis of cyclophane-containing complex 49 through Glaser–Eglinton coupling reaction. Reagents a...
Scheme 8: Synthesis of cyclophane 53 through Glaser–Eglinton coupling. Reagents and conditions: (i) K2CO3, ac...
Figure 6: Cyclophanes 54–56 that have been synthesized through Glaser–Eglinton coupling.
Figure 7: Synthesis of tetrasubstituted [2.2]paracyclophane 57 and chiral cyclophyne 58 through Eglinton coup...
Scheme 9: Synthesis of cyclophane through Glaser–Hay coupling reaction. Reagents and conditions: (i) CuCl2 (1...
Scheme 10: Synthesis of seco-C/D ring analogs of ergot alkaloids through intramolecular Heck reaction. Reagent...
Scheme 11: Synthesis of muscopyridine 73 via Kumada coupling. Reagents and conditions: (i) 72, THF, ether, 20 ...
Scheme 12: Synthesis of the cyclophane 79 via McMurry coupling. Reagents and conditions: (i) 75, decaline, ref...
Scheme 13: Synthesis of stilbenophane 81 via McMurry coupling. Reagents and conditions: (i) TiCl4, Zn, pyridin...
Scheme 14: Synthesis of stilbenophane 85 via McMurry coupling. Reagents and conditions: (i) NBS (2 equiv), ben...
Figure 8: List of cyclophanes prepared via McMurry coupling reaction as a key step.
Scheme 15: Synthesis of paracyclophane by cross coupling involving Pd(0) catalyst. Reagents and conditions: (i...
Scheme 16: Synthesis of the cyclophane 112 via the pinacol coupling and 113 by RCM. Reagents and conditions: (...
Scheme 17: Synthesis of cyclophane derivatives 122a–c via Sonogoshira coupling. Reagents and conditions: (i) C...
Scheme 18: Synthesis of cyclophane 130 via Suzuki–Miyaura reaction as a key step. Reagents and conditions: (i)...
Scheme 19: Synthesis of the mycocyclosin via Suzuki–Miyaura cross coupling. Reagents and conditions: (i) benzy...
Scheme 20: Synthesis of cyclophanes via Wurtz coupling reaction Reagents and conditions: (i) PhLi, Et2O, C6H6,...
Scheme 21: Synthesis of non-natural glycophanes using alkyne metathesis. Reagents and conditions: (i) G-I (12)...
Figure 9: Synthesis of cyclophanes via ring-closing alkyne metathesis.
Scheme 22: Synthesis of crownophanes by cross-enyne metathesis. Reagents and conditions: (i) G-II (13), 5 mol ...
Scheme 23: Synthesis of (−)-cylindrocyclophanes A (156) and (−)-cylindrocyclophanes F (155). Reagents and cond...
Scheme 24: Synthesis of cyclophane 159 derivatives via SM cross-coupling and RCM. Reagents and conditions: (i)...
Scheme 25: Sexithiophene synthesis via cross metathesis. Reagents and conditions: (i) 161, Pd(PPh3)4, K2CO3, T...
Scheme 26: Synthesis of pyrrole-based cyclophane using enyne metathesis. Reagents and conditions: (i) Se, chlo...
Scheme 27: Synthesis of macrocyclic derivatives by RCM. Reagents and conditions: (i) G-I/G-II, CH2Cl2, 0.005 M...
Scheme 28: Synthesis of enantiopure β-lactam-based dienyl bis(dihydrofuran) 179. Reagents and conditions: (i) ...
Scheme 29: Synthesis of a [1.1.6]metaparacyclophane derivative 183 via SM cross coupling. Reagents and conditi...
Scheme 30: Synthesis of a [1.1.6]metaparacyclophane derivative 190 via SM cross coupling. Reagents and conditi...
Scheme 31: Template-promoted synthesis of cyclophanes involving RCM. Reagents and conditions: (i) acenaphthene...
Scheme 32: Synthesis of [3.4]cyclophane derivatives 200 via SM cross coupling and RCM. Reagents and conditions...
Figure 10: Examples for cyclophanes synthesized by RCM.
Scheme 33: Synthesis of the longithorone C framework assisted by fluorinated auxiliaries. Reagents and conditi...
Scheme 34: Synthesis of the longithorone framework via RCM. Reagents and conditions: (i) 213, NaH, THF, rt, 10...
Scheme 35: Synthesis of floresolide B via RCM as a key step. Reagents and conditions: (i) G-II (13, 0.1 equiv)...
Scheme 36: Synthesis of normuscopyridine (223) by the RCM strategy. Reagents and condition: (i) Mg, THF, hexen...
Scheme 37: Synthesis of muscopyridine (73) via RCM. Reagents and conditions: (i) 225, NaH, THF, 0 °C to rt, 1....
Scheme 38: Synthesis of muscopyridine (73) via RCM strategy. Reagents and conditions: (i) NaH, n-BuLi, 5-bromo...
Scheme 39: Synthesis of pyridinophane derivatives 223 and 245. Reagents and conditions: (i) PhSO2Na, TBAB, CH3...
Scheme 40: Synthesis of metacyclophane derivatives 251 and 253. Reagents and conditions: (i) 240, NaH, THF, rt...
Scheme 41: Synthesis of normuscopyridine and its higher analogues. Reagents and conditions: (i) alkenyl bromid...
Scheme 42: Synthesis of fluorinated ferrocenophane 263 via a [2 + 2] cycloaddition. Reagents and conditions: (...
Scheme 43: Synthesis of [2.n]metacyclophanes 270 via a [2 + 2] cycloaddition. Reagents and conditions: (i) Ac2...
Scheme 44: Synthesis of metacyclophane 273 by a [2 + 2 + 2] co-trimerization. Reagents and conditions: (i) [Rh...
Scheme 45: Synthesis of paracyclophane 276 via a [2 + 2 + 2] cycloaddition reaction. Reagents and conditions: ...
Scheme 46: Synthesis of cyclophane 278 via a [2 + 2 + 2] cycloaddition reaction. Reagents and conditions: (i) ...
Scheme 47: Synthesis of cyclophane 280 via a [2 + 2 + 2] cycloaddition. Reagents and conditions: (i) [(Rh(cod)(...
Scheme 48: Synthesis of taxane framework by a [2 + 2 + 2] cycloaddition. Reagents and conditions: (i) Cp(CO)2 ...
Scheme 49: Synthesis of cyclophane 284 and 285 via a [2 + 2 + 2] cycloaddition reaction. Reagents and conditio...
Scheme 50: Synthesis of pyridinophanes 293a,b and 294a,b via a [2 + 2 + 2] cycloaddition. Reagents and conditi...
Scheme 51: Synthesis of pyridinophanes 296 and 297 via a [2 + 2 + 2] cycloaddition. Reagents and conditions: (...
Scheme 52: Synthesis of triazolophane by a 1,3-dipolar cycloaddition. Reagents and conditions: (i) propargyl b...
Scheme 53: Synthesis of glycotriazolophane 309 by a click reaction. Reagents and conditions: (i) LiOH, H2O, Me...
Figure 11: Cyclophanes 310 and 311 prepared via click chemistry.
Scheme 54: Synthesis of cyclophane via the Dötz benzannulation. Reagents and conditions: (i) THF, 100 °C, 12 h...
Scheme 55: Synthesis of [6,6]metacyclophane by a Dötz benzannulation. Reagents and conditions: (i) THF, 100 °C...
Scheme 56: Synthesis of cyclophanes by a Dötz benzannulation. Reagents and conditions: (i) THF, 65 °C, 3 h; (i...
Scheme 57: Synthesis of muscopyridine (73) via an intramolecular DA reaction of ketene. Reagents and condition...
Scheme 58: Synthesis of bis[10]paracyclophane 336 via Diels–Alder reaction. Reagents and conditions: (i) DMAD,...
Scheme 59: Synthesis of [8]paracyclophane via DA reaction. Reagents and conditions: (i) maleic anhydride, 3–5 ...
Scheme 60: Biomimetic synthesis of (−)-longithorone A. Reagents and conditions: (i) Me2AlCl, CH2Cl2, −20 °C, 7...
Scheme 61: Synthesis of sporolide B (349) via a [4 + 2] cycloaddition reaction. Reagents and conditions: (i) P...
Scheme 62: Synthesis of the framework of (+)-cavicularin (352) via a [4 + 2] cycloaddition. Reagents and condi...
Scheme 63: Synthesis of oxazole-containing cyclophane 354 via Beckmann rearrangement. Reagents and conditions:...
Scheme 64: Synthesis of cyclophanes 360a–c via benzidine rearrangement. Reagents and conditions: (i) 356a–d, K2...
Scheme 65: Synthesis of cyclophanes 365a–c via benzidine rearrangement. Reagents and conditions: (i) BocNHNH2,...
Scheme 66: Synthesis of metacyclophane 367 via Ciamician–Dennstedt rearrangement. Reagents and conditions: (i)...
Scheme 67: Synthesis of cyclophane by tandem Claisen rearrangement and RCM as key steps. Reagents and conditio...
Scheme 68: Synthesis of cyclophane derivative 380. Reagents and conditions: (i) K2CO3, CH3CN, allyl bromide, r...
Scheme 69: Synthesis of metacyclophane via Cope rearrangement. Reagents and conditions: (i) MeOH, NaBH4, rt, 1...
Scheme 70: Synthesis of cyclopropanophane via Favorskii rearrangement. Reagents and conditions: (i) Br2, CH2Cl2...
Scheme 71: Cyclophane 389 synthesis via photo-Fries rearrangement. Reagents and conditions: (i) DMAP, EDCl/CHCl...
Scheme 72: Synthesis of normuscopyridine (223) via Schmidt rearrangement. Reagents and conditions: (i) ethyl s...
Scheme 73: Synthesis of crownophanes by tandem Claisen rearrangement. Reagents and conditions: (i) diamine, Et3...
Scheme 74: Attempted synthesis of cyclophanes via tandem Claisen rearrangement and RCM. Reagents and condition...
Scheme 75: Synthesis of muscopyridine via alkylation with 2,6-dimethylpyridine anion. Reagents and conditions:...
Scheme 76: Synthesis of cyclophane via Friedel–Craft acylation. Reagents and conditions: (i) CS2, AlCl3, 7 d, ...
Scheme 77: Pyridinophane 418 synthesis via Friedel–Craft acylation. Reagents and conditions: (i) 416, AlCl3, CH...
Scheme 78: Cyclophane synthesis involving the Kotha–Schölkopf reagent 421. Reagents and conditions: (i) NBS, A...
Scheme 79: Cyclophane synthesis involving the Kotha–Schölkopf reagent 421. Reagents and conditions: (i) BEMP, ...
Scheme 80: Cyclophane synthesis by coupling with TosMIC. Reagents and conditions: (i) (a) ClCH2OCH3, TiCl4, CS2...
Scheme 81: Synthesis of diaza[32]cyclophanes and triaza[33]cyclophanes. Reagents and conditions: (i) DMF, NaH,...
Scheme 82: Synthesis of cyclophane 439 via acyloin condensation. Reagents and conditions: (i) Na, xylene, 75%;...
Scheme 83: Synthesis of multibridged binuclear cyclophane 442 by aldol condensation. Reagents and conditions: ...
Scheme 84: Synthesis of various macrolactones. Reagents and conditions: (i) iPr2EtN, DMF, 77–83%; (ii) TBDMSCl...
Scheme 85: Synthesis of muscone and muscopyridine via Yamaguchi esterification. Reagents and conditions: (i) 4...
Scheme 86: Synthesis of [5]metacyclophane via a double elimination reaction. Reagents and conditions: (i) LiBr...
Figure 12: Cyclophanes 466–472 synthesized via Hofmann elimination.
Scheme 87: Synthesis of cryptophane via Baylis–Hillman reaction. Reagents and conditions: (i) methyl acrylate,...
Scheme 88: Synthesis of cyclophane 479 via double Chichibabin reaction. Reagents and conditions: (i) excess 478...
Scheme 89: Synthesis of cyclophane 483 via double Chichibabin reaction. Reagents and conditions: (i) 481, OH−;...
Scheme 90: Synthesis of cyclopeptide via an intramolecular SNAr reaction. Reagents and conditions: (i) TBAF, T...
Scheme 91: Synthesis of muscopyridine (73) via C-zip ring enlargement reaction. Reagents and conditions: (i) H...
Figure 13: Mechanism of the formation of compound 494.
Scheme 92: Synthesis of indolophanetetraynes 501a,b using the Nicholas reaction as a key step. Reagents and co...
Scheme 93: Synthesis of cyclophane via radical cyclization. Reagents and conditions: (i) cyclododecanone, phen...
Scheme 94: Synthesis of (−)-cylindrocyclophanes A (156) and (−)-cylindrocyclophanes F (155). Reagents and cond...
Scheme 95: Cyclophane synthesis via Wittig reaction. Reagents and conditions: (i) LiOEt (2.1 equiv), THF, −78 ...
Figure 14: Representative examples of cyclophanes synthesized via Wittig reaction.
Scheme 96: Synthesis of the [6]paracyclophane via isomerization of Dewar benzene. Reagents and conditions: (i)...
