Enzymelike Catalysis of the Nazarov Cyclization by Supramolecular Encapsulation
Enzymelike Catalysis of the Nazarov Cyclization by Supramolecular Encapsulation
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DOI：
10.1021/ja102633e
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发表时间：
2010-05-26
影响因子：
15
通讯作者：
Raymond, Kenneth N.
中科院分区：
文献类型：
--
作者：
Hastings, Courtney J.;Pluth, Michael D.;Raymond, Kenneth N.
水溶性、自组装的四面体组装体K12Ga4L6 （L = 1,5-双儿茶酚氨基萘）以极高的效率催化1,3-戊二烯醇的Nazarov环化。催化反应的进行速度比背景反应快100多万倍，与在某些酶系统中观察到的速度相当。这种催化作用在温和的温度和pH值的水条件下进行，并通过添加适当的抑制剂来停止反应。这种前所未有的速率提高是由于质子化反应中间体的稳定和对结合客体的收缩结合的影响。
The water-soluble, self-assembled, tetrahedral assembly K12Ga4L6 (L = 1,5-biscatecholamidenaphthalene) catalyzes the Nazarov cyclization of 1,3-pentadienols with extremely high levels of efficiency. The catalyzed reaction proceeds over a million times faster than the background reaction, an increase comparable to those observed in some enzymatic systems. This catalysis operates under aqueous conditions at mild temperatures and pH, and the reaction is halted by the addition of an appropriate inhibitor. This unprecedented rate enhancement is attributed to both the stabilization of protonated reaction intermediates and the effect of constrictive binding on the bound guest.