0000000000400504
AUTHOR
Guy Yves Vollmer
Synthesis, characterization and X-ray crystal structures of cyclam derivatives. Part VI. Proton binding studies of a pyridine-strapped 5,12-dioxocyclam based macrobicycle
The 14-membered cyclic diamide 1,4,8,11-tetraazacyclotetradecane-5,12-dione (5,12-dioxocyclam) can be considered as a trans-autodiprotected tetraazamacrocycle and provides a convenient starting material for the preparation of macrobicyclic receptors. As an example, the secondary amine nitrogen atoms located at the 1 and 8 positions were cross-bridged with a 1,3-pyridyl strap, affording the constrained ansa-dioxocyclam ligand 1,9,12,18,22-pentaazatricyclo[7.6.6.13,7]docosa-3,5,7(22)-triene-13,19-dione (L1). The proton binding properties of this cage-type compound, which possesses a hemispherical cavity, were fully investigated by spectroscopic (IR, NMR, UV, MALDI-TOF MS), quantum chemical, a…
Synthesis, characterization and X-ray crystal structures of cyclam derivatives. 7. Hydrogen-bond induced allosteric effects and protonation cooperativity in a macrotricyclic bisdioxocyclam receptor
The unprecedented cooperative protonation properties displayed by a barrel-shaped macrotricyclic tetraamine incorporating two 14-membered bisamide rings maintained in a face-to-face arrangement is rationalized in terms of allosteric effects upon binding of the first and third protons.