DNA-Accelerated Copper Catalysis of Friedel–Crafts Conjugate Addition/Enantioselective Protonation Reactions in Water

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• 作者：Almudena García-Fernández ; Rik P. Megens ; Lara Villarino ; Gerard Roelfes
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：December 21, 2016
• 年：2016
• 卷：138
• 期：50
• 页码：16308-16314
• 全文大小：417K
• ISSN：1520-5126

文摘

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.