脲嘧啶酮与2,7-二氨基萘啶的络合机制以及多组分氢键体系中动力学控制途径的存在。

The mechanism of ureido-pyrimidinone:2,7-diamido-naphthyridine complexation and the presence of kinetically controlled pathways in multicomponent hydrogen-bonded systems.

作者信息

de Greef Tom F A, Ligthart G B W L, Lutz Martin, Spek Anthony L, Meijer E W, Sijbesma Rint P

机构信息

Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands.

出版信息

J Am Chem Soc. 2008 Apr 23;130(16):5479-86. doi: 10.1021/ja709971y. Epub 2008 Mar 29.

DOI:10.1021/ja709971y

PMID:18373340

Abstract

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.

摘要

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。