Stratingh Institute for Chemistry, University of Groningen , Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
J Am Chem Soc. 2016 Dec 21;138(50):16308-16314. doi: 10.1021/jacs.6b08295. Epub 2016 Dec 6.
DNA-induced rate acceleration has been identified as one of the key elements for the success of the DNA-based catalysis concept. Here we report on a novel DNA-based catalytic Friedel-Crafts conjugate addition/enantioselective protonation reaction in water, which represents the first example of a reaction that critically depends on the >700- to 990-fold rate acceleration caused by the presence of a DNA scaffold. The DNA-induced rate acceleration observed is the highest reported due to the environment presented by a biomolecular scaffold for any hybrid catalyst, to date. Based on a combination of kinetics and binding studies, it is proposed that the rate acceleration is in part due to the DNA acting as a pseudophase, analogous to micelles, in which all reaction components are concentrated, resulting in a high effective molarity. The involvement of additional second coordination sphere interactions is suggested by the enantioselectivity of the product. The results presented here show convincingly that the DNA-based catalysis concept, thanks to the DNA-accelerating effect, can be an effective approach to achieving a chemically challenging reaction in water.
DNA 诱导的速率加速已被确定为 DNA 催化概念成功的关键因素之一。在这里，我们报告了一种新型的基于 DNA 的催化傅克加成/对映选择性质子化反应在水中，这代表了第一个关键依赖于 DNA 支架引起的 >700 至 990 倍速率加速的反应的例子。由于生物分子支架为任何混合催化剂提供的环境，所观察到的 DNA 诱导的速率加速是迄今为止报道的最高的。基于动力学和结合研究的结合，据推测，部分速率加速是由于 DNA 作为类似胶束的假相起作用，其中所有反应成分都被浓缩，导致高有效摩尔浓度。产物的对映选择性表明存在额外的第二配位层相互作用。这里呈现的结果令人信服地表明，基于 DNA 的催化概念，由于 DNA 加速效应，可以成为在水中实现具有化学挑战性的反应的有效方法。
