The mechanism of ureido-pyrimidinone:2,7-diamido-naphthyridine complexation and the presence of kinetically controlled pathways in multicomponent hydrogen-bonded systems.
The kinetics of association of ureido-pyrimidinone (U) dimers, present either in the 4[1H]-keto form or in the pyrimidin-4-ol form, with 2,7-diamido-1,8-naphthyridine (N) into a complementary heterodimer have been investigated. The formation of heterodimers with 2,7-diamido-1,8-naphthyridine from pyrimidin-4-ol dimers is much faster than from 4[1H]-pyrimidinone dimers. Using a combination of simple measurements and simulations, evidence for a bimolecular tautomerization step is presented. Finally, the acquired kinetic knowledge of the different pathways leading from ureido-pyrimidinone homodimers to ureido-pyrimidinone:diamido-naphthyridine (U:N) heterodimers allows the prediction and observation of kinetically determined ureido-pyrimidinone heterodimers which slowly convert back to the corresponding homodimers.
de Greef
Tom F A
TF
Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
Ligthart
G B W L
GB
Lutz
Martin
M
Spek
Anthony L
AL
Meijer
E W
EW
Sijbesma
Rint P
RP
D001665:Binding Sites; D003958:Diamide / Q000031:analogs & derivatives*; D019281:Dimerization; D006860:Hydrogen Bonding; D007700:Kinetics; D009287:Naphthyridines / Q000737:chemistry*; D011744:Pyrimidinones / Q000737:chemistry*; D014508:Urea / Q000031:analogs & derivatives*
D009287:Naphthyridines; D011744:Pyrimidinones; D003958:Diamide; D014508:Urea