Multiple Catenanes Derived from Calix[4]arenes

A multicatenane is described in which two belts consisting of four annelated rings attached to the wide rims of two calix[4]arenes are interwoven in such a way that each ring of one belt penetrates two adjacent rings of the other belt and vice versa. The key step of the synthesis of this [8]catenane is the exclusive formation of preorganized heterodimers between a multimacrocyclic tetraurea calix[4]arene and an “open-chain” tetraurea calix[4]arene containing eight ω-alkenyl groups. When a tetraurea calix[4]arene containing four alkenyl groups is used, a bis-[3]catenane is formed analogously.

Synthesis of huge macrocycles using two calix[4]arenes as templates.

Macrocycles with up to 100 atoms have been synthesised using two calix[4]arenes as templates: first, (3,5-dialkenyloxy)phenyl groups are attached to the wide rim of a calix[4]arene via urea links, then the alkenyl groups are connected via a metathesis reaction using a tetratosylurea calix[4]arene for their correct prearrangement and finally the urea functions are cleaved to detach the newly formed macrocycles.

Narrow rim CMPO/adamantylcalix[4]arenes for the extraction of lanthanides and actinides

Abstract Six p-(1-adamantyl)calix[4]arenes 7, 8 with four differently attached diphenyl-carbamoylmethylphosphine oxide (CMPO) functions at the narrow rim were synthesized. This series was extended by adamantylcalix[4]arenes with two CMPO and two ester, acid or (diethylphosphono)acetylamino groups. Structures of new compounds were proved by NMR, mass-spectrometry and a single-crystal X-ray analysis for the intermediate di-phthalimide 103. The extraction studies towards selected lanthanides and thorium showed that the ligands 7 surpassed the corresponding p-H, p-tert-butyl and p-tert-octyl analogues 3–5 in lanthanide extraction while thorium was extracted with the same or lesser extent. For t…

Template synthesis of multi-macrocycles by metathesis reaction.

Selective heterodimerisation of tetraurea calix[4]arenes containing four or eight ω-alkenyl groups with a tetratosyl urea calix[4]arene has been effectively used to synthesize multi-macrocycles via metathesis reaction.

Template Synthesis of Multi-Macrocycles by Metathesis Reactions.

Synthesis of a macrobicycle incorporating the tris(pyrazolyl)methane ligand.

Steric crowding of the 3-position of tris(pyrazolyl)borate and -methane ligands has produced tetrahedral metal complexes with controlled reactivity. As an alternative, we propose to incorporate the tris(pyrazolyl)methane chelate in a macrobicyclic structure in order to create a cavity with well-defined dimensions and shape. Acid-catalyzed equilibration of excess of the new pyrazole 3-(1H-pyrazol-3-yl)benzenemethanethiol acetate with HC(3,5-Me(2)pz)(3) followed by hydrolysis affords a functionalized tris(pyrazolyl)methane, which reacts with 1,3,5-tris(bromomethyl)benzene in K(2)CO(3)/DMF to give the title compound. [structure: see text]

Versatility and dynamics of the copper(I) coordination sphere in sterically hindering tris(pyrazolyl)methane-incorporating macrobicycles

Two arene-capped macrobicycles (1 and 2) incorporating the tris(pyrazolyl)methane (Tpm) chelate have been prepared from a benzylthiol-functionalized Tpm precursor (3). Reaction of either macrobicycle with Cu(CH3CN)4+ leads to tetrahedral or trigonal-planar, fluxional complexes incorporating the Cu(CH3CN)+ subunit ([Cu(1)(CH3CN)]+ and [Cu(2)(CH3CN)]+). The acetonitrile ancillary ligand does not fit inside the macrobicycle cavity and can be removed by heating under vacuum, which produces the [Cu(1)]+ and [Cu(2)]+ species probably involving intramolecular thioether coordination. The [Cu(1)(CH3CN)]+ complex was shown to convert slowly in wet acetone into a helical coordination polymer, which is…

CCDC 710459: Experimental Crystal Structure Determination

Related Article: Leyong Wang, J.-C.Chambron, E.Espinosa|2009|New J.Chem.|33|327|doi:10.1039/b816275a

CCDC 814605: Experimental Crystal Structure Determination

Related Article: I.Vatsouro, A.Serebryannikova, Leyong Wang, V.Hubscher-Bruder, E.Shokova, M.Bolte, F.Arnaud-Neu, V.Bohmer, V.Kovalev|2011|Tetrahedron|67|8092|doi:10.1016/j.tet.2011.08.059

CCDC 710458: Experimental Crystal Structure Determination

Related Article: Leyong Wang, J.-C.Chambron, E.Espinosa|2009|New J.Chem.|33|327|doi:10.1039/b816275a

CCDC 265476: Experimental Crystal Structure Determination

Related Article: Yudong Cao, Leyong Wang, M.Bolte, M.O.Vysotsky, V.Bohmer|2005|Chem.Commun.||3132|doi:10.1039/b505223h