通过在串联DNA催化的傅克烷基化/不对称质子化反应中精确配体定位来合理寻求选择性。

Mansot Justine, Aubert Sidonie, Duchemin Nicolas, Vasseur Jean-Jacques, Arseniyadis Stellios, Smietana Michael

Institut des Biomolécules Max Mousseron , CNRS , Université de Montpellier , ENSCM , Place Eugène Bataillon , 34095 Montpellier , France . Email:

School of Biological and Chemical Sciences , Queen Mary University of London , Joseph Priestley Building, Mile End Road , London E1 4NS , UK . Email:

Chem Sci. 2019 Jan 24;10(10):2875-2881. doi: 10.1039/c8sc05543b. eCollection 2019 Mar 14.

Covalent anchorage of a metallic co-factor to a DNA-based architecture is merely the only way to ensure an accurate positioning of a catalytic site within the chiral micro-environment offered by the DNA double helix. Ultimately, it also allows a fine-tuning of the catalytic pocket through simple synthetic modifications of the DNA sequence. Here, we report highly selective copper(ii)-catalysed asymmetric Friedel-Crafts conjugate addition/enantioselective protonation, which is due to a careful positioning of a bipyridine ligand within a DNA framework. Most importantly, this study unveils specific structural features that account for an optimal chirality transfer from the duplex to the Friedel-Crafts adducts.

将金属辅因子共价固定到基于DNA的结构上，是确保催化位点在DNA双螺旋提供的手性微环境中准确定位的唯一方法。最终，它还能通过对DNA序列进行简单的合成修饰来微调催化口袋。在此，我们报道了高度选择性的铜（II）催化的不对称傅克共轭加成/对映选择性质子化反应，这是由于联吡啶配体在DNA骨架中的精确位置所致。最重要的是，这项研究揭示了特定的结构特征，这些特征解释了从双链体到傅克加合物的最佳手性转移。