Macrocyclic Cyclophane Research Articles

Enantiopure C1-Cyclotriveratrylene with a Reversed Spatial Arrangement of the Substituents.

Cyclotriveratrylene (CTV) is a macrocyclic cyclophane presenting a bowl-shaped conformation, used as building block to construct cryptophane and hemicryptophane capsules. A method to synthesize new enantiopure CTV derivatives with an unprecedented spatial arrangement of their substituents, exhibiting C1 symmetry, is described. The absolute configuration was assigned by ECD spectroscopy coupled with modeling. A statistical model has allowed for optimization of the proportion of C1 CTV, and the modularity of this approach is also highlighted.

Diversity-Oriented Approach to Macrocyclic Cyclophane Derivatives via Ring-Closing Metathesis

A short synthetic approach to the macrocyclic framework of longithorone C is described via ring-closing metathesis using the Grubbs 2nd generation catalyst.

Diversity-Oriented Approach to Macrocyclic Cyclophane Derivatives by Suzuki–Miyaura Cross-Coupling and Olefin Metathesis as Key Steps

Palladium-catalyzed Suzuki-Miyaura (SM) cross-coupling reaction with allylboronic acid pinacol ester and titanium assisted cross-metathesis (CM)/ring-closing metathesis (RCM) cascade has been used to synthesize macrocyclic cyclophane derivatives.

Synthesis of macrocyclic cyclophane-based unusual α-amino acid derivatives

Alkylation of ethyl isocyanoacetate with 1,2-bis(4-bromomethylphenyl)ethane under phase transfer catalysis (PTC) as well as phosphazene base (2-tert-butylimino-2-diethylamino-1,3- dimethylperhydro-1,3,2-diazaphosphorine (BEMP)) conditions gave the macrocyclic cyclophane based unusual α-amino acid derivatives.

Molecular and Crystal Structure of a Bisanthracene-9,10-diyl Macrocyclic Coronand AAO5O5 and of its Bis-1,4-endoperoxide, a Bistetraoxapaddlane

AAO5O5 3, a bisanthracene macrocyclic cyclophane, is known to be an excimer-type fluorosensor for sodium cations and to encapsulate electron-deficient species such as paraquat. Its bis-1,4-endoperoxide 4 is a tetraoxapaddlane. The molecular and crystal structures of 3 and 4 are described.

Macrocyclic cyclophane belts via double Diels-Alder cycloadditions: Macroannulation of bisdienes by bisdienophiles. Synthesis of a key precursor to an [8]cyclacene

A synthesis of macrocyclic cyclophanes is accomplished by double Diels-Alder cycloaddition of two bisdienophiles, 1,4,5,8-anthradiquinone and p-phenylenedimaleimide, to a bisdiene, 2,3,6,7-tetraheptylidene-1,2,3,4,5,6,7,8-octahydroanthracene. The structure of the macrocyclic cyclophane derived from the diquinone has been determined by single crystal x-ray diffraction, in addition to 1H and 13C NMR, HRMS and IR spectroscopic data.

Transformations of a macrocyclic cyclophane belt into advanced [8]cyclacene and [8]cyclacene triquinone precursors

Belt-shaped cyclophane 2, is converted to a naphthalene-containing belt-shaped cyclophane by dehydrogenation, to an unexpected bisdiene-containing belt-shaped cyclophane by epoxidation and dehydration, and to an unexpected anthraquinone-containing belt-shaped cyclophane by PCC oxidation. The latter cyclophane could be functionalized further by a surprising oxidation involving sequential dehydrogenation and conjugate addition of ethoxide.

A self-organised layered superstructure of arrayed [2]pseudorotaxanes

A [2]pseudorotaxane, built up from a macrocyclic cyclophane containing two atomatic π-acceptors and an acyclic molecular containing three aromatic π-donors, has the ability to undergo self-organisation on crystallisation to form a layered superstructure of arrayed [2]pseudorotaxanes.

ChemInform Abstract: A New Macrocyclic Cyclophane Incorporating Three Naphthalene and One Anthracene Units. Crystal Structure and Fluorescence Quenching by Th4+ and Other Metal Cations.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Anion complexes between a macrocyclic cyclophane and squaric acid: The crystal structure reveals the ideal receptor topology ordered by the substrate

Abstract The expected [1:2] complex between a tetraprotonated tetraazapara-cyclophane and squaric acid is not formed and the ligand undergoes drastic deformation. The peculiar features of this structure is the coexistence, in the same crystal cell, of 2 types of crystal lattice inclusions, corresponding to 2 different dissociation modes of squaric acid.

Triquinane-derived macrocyclic cyclophane hosts

A one step stereoselective assembly of novel macrocyclic cyclophane hosts 4a and b from readily available cis,syn,cis-triquinane dione and 4,4′-dianilinoalkanes is described.

3.2]Paracyclophane‐10‐enes and [3.2.3.2]Paracyclophane‐10,27‐dienes: A convenient synthesis by the McMurry reaction and dynamic stereochemistry

AbstractThe 1,3‐bis(4‐acylphenyl)propanes 2, 3, 9, 12, and 15 were subjected to a cyclization by reductive coupling with low‐valent titanium (McMurry reaction). 2 and 3 are converted into the corresponding 10,11‐dialkyl[3.2]paracyclophane‐10‐enes 4 and 5, respectively, under carefully controlled conditions in good yields. By the same method the dialdehydes 12 and 15 give rise to [3.2]paracyclophane‐10‐ene 13 and [3.2]metacyclophane‐10‐ene 16. However, the ditoluoyl derivative 9 gives rise only to the macrocyclic cyclophane 10 by dimerization. The corresponding macrocyclic cyclophanes 6 and 7 were also obtained from 2 and 3, respectively. The conformational mobility of the cyclophanes 4,5, and 13 was studied by variable‐temperature 1H‐NMR, and ΔG≠ = 48–51 KJ/mol was determined for the wobbling motion of the propano bridges.

大環状シクロファン包接体の構造

The crystallographic study of macrocyclic cyclophane inclusion compounds is reviewed. Cyclophanes such as [2.2.2], [6.6.6], [3.3.3.3] and [6.1.6.1] paracyclophanes and calixarenes with intramolecular hydrophobic cavities surrounded by benzene walls incorporate neutral guest molecules to give molecular inclusion compounds (cavitate) in solutions and in the solid state. Tri-o-thymotide forms chiral single crystals of cage type or channel type clathrate which have enantiomeric excess of guest molecules. [J. Cryst. Soc. Jpn. 28, 261 (1986) ] .

ChemInform Abstract: SYNTHESIS OF MACROCYCLIC (N.N.N)(1,3,5)CYCLOPHANE POLYLACTONES

AbstractDie Darstellung der Cyclophan‐Polylactone (III) und (V) erfolgt durch die einstufige Kondensation der entsprechenden Säurechloride (I) mit den Triolen (II) bzw. (IV) in Gegenwart von AgCN bei hoher Verdünnung.

Synthesis of Macrocyclic [n.n.n](1,3,5)Cyclophane Polylactones

Abstract A series of new macrocyclic cyclophane polylactones has been synthesized by one-step condensation of the appropriate tri(acid chloride)s and triols using the silver cyanide-promoted esterification procedure.