de Greef Tom F A, Ligthart G B W L, Lutz Martin, Spek Anthony L, Meijer E W, Sijbesma Rint P
Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
J Am Chem Soc. 2008 Apr 23;130(16):5479-86. doi: 10.1021/ja709971y. Epub 2008 Mar 29.
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.
对以4[1H]-酮形式或嘧啶-4-醇形式存在的脲嘧啶酮（U）二聚体与2,7-二氨基-1,8-萘啶（N）缔合形成互补异二聚体的动力学进行了研究。由嘧啶-4-醇二聚体形成与2,7-二氨基-1,8-萘啶的异二聚体比由4[1H]-嘧啶酮二聚体形成的速度快得多。通过简单测量和模拟相结合的方法，给出了双分子互变异构步骤的证据。最后，所获得的关于从脲嘧啶酮同二聚体到脲嘧啶酮：二氨基萘啶（U:N）异二聚体的不同途径的动力学知识，使得能够预测和观察动力学决定的脲嘧啶酮异二聚体，它们会缓慢地转化回相应的同二聚体。
