6533b7d6fe1ef96bd1266478
RESEARCH PRODUCT
Synthesis of Macropolycyclic Ligands Based on Tetraazacycloalkanes
Sylvie LacourRoger GuilardPluton PullumbiFrédéric BarbetteFrédéric RabietStéphane BrandèsFranck Denatsubject
Reaction conditionschemistry.chemical_compoundCyclenChemistryStereochemistryOrganic ChemistryCyclamRigid structureProtonationPhysical and Theoretical ChemistrySelectivityCombinatorial chemistrydescription
A versatile synthesis of spherical macrobicyclic and cylindrical macrotricyclic ligands is described using 1,4,8,11-tetraazacyclotetradecane (cyclam), 1,4,7,10-tetraazacyclododecane (cyclen), or dioxo macrocycles as precursors. Macrobicycles have been obtained by allowing cyclam, cyclen, or 5,12-dioxocyclam (1,4,8,11-tetraazacyclotetradecane-5,12-dione) to react with a bis-electrophilic spacer under high dilution conditions. A surprising selectivity has been observed for 2,6-dioxocyclen (1,4,7,10-tetraazacyclododecane-2,6-dione), which yields only macrotricycles under the same reaction conditions. Molecular modelling studies have been carried out to investigate the selectivity of the reactions, and good agreement has been observed between the theoretical predictions and experimental data. 1D- and 2D-NMR studies reveal a highly rigid structure in the case of macrobicycles. The macropolycyclic ligands show very different basicities, which demonstrates the influence of the cross-linker on the coordination properties of the ligands.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 1998-11-01 | European Journal of Organic Chemistry |