Synthesis, NMR and X-Ray Structure of Phosphorylated Tetram Eric Metacyclophanes

Syntheses, characterization, stereochemistry and complexing properties of acyclic and macrocyclic compounds possessing ?-amino- or ?-hydroxyphosphonate units: a review article

“…This was affected in order to make use of robust macrocycles XIV and XV (Chart 3) that are able to complex cations, and, in particular, lanthanides, useful as luminescent sensors and for diagnostic bioassays [8,9,40] in powerful screening techniques such as magnetic resonance imaging (MRI) and in proton emission computed assisted tomography (SPECT). Macrocycles XIV and XV were fully characterized by NMR and by FABMS spectroscopy, and their stereochemistry was investigated in solution and also in the solid state for compound XIVb [38,39]. The NMR data are consistent with a 1,3-alternated saddle-shaped geometry, and the inner methyl groups are very much upfield shifted by the aromatic ring current effect.…”

“…Therefore, we functionalized some of such macrocycles by use of the insertion of pendant methylene phosphonic acid dialkyl ester groups, by the Arbuzov reaction starting from the chloromethyl derivatives [38,39]. This was affected in order to make use of robust macrocycles XIV and XV (Chart 3) that are able to complex cations, and, in particular, lanthanides, useful as luminescent sensors and for diagnostic bioassays [8,9,40] in powerful screening techniques such as magnetic resonance imaging (MRI) and in proton emission computed assisted tomography (SPECT).…”

“…The cyclohexane molecule incorporated into the crystal structure, does not appear as a molecular inclusion compound, but rather as a lattice clathrate. Specifically, and as an unusual feature, the cyclohexane molecules are arranged in a tetrahedron-like cluster of four around a 222-D 2 position of the space group at 1/4, 3/4, 1/2 (and 3/4, 1/4, 1/2) [38].…”

Phosphorus-containing macrocyclic compounds: synthesis and properties

“…161 e. Phosphorylation of meta-and paracyclophanes The phosphorylation of macrocycles related to calix [4]arenes, viz., tetrameric metacyclophanes containing four methylene-bridged aromatic units was documented. 162 The Arbuzov reaction with the participation of chloromethylated cyclophane 195 and trialkylphosphites afforded phosphorus-containing tetrameric analogues of calix [4]arenes 196 (Scheme 68).…”

Coordination Compounds Based on Metacyclophane Derivatives

“…Different chemical modifications of the [1.1.1.1]metacyclophane backbones have been proposed in the literature: tetrasubstitution with appending chiral [13] and diethylphosphonate [14] groups, formation of doubly crowned metacyclophane [15] and Schiff base [16] derivatives have been reported. Synthesis of nitroxide tetrasubstituted compound presenting some interesting magnetic properties has also been described.…”