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A rational quest for selectivity through precise ligand-positioning in tandem DNA-catalysed Friedel-Crafts
Justine Mansot1, Sidonie Aubert2, Nicolas Duchemin2
1Institut des Biomolécules Max Mousseron , CNRS , Université de Montpellier , ENSCM , Place Eugène Bataillon , 34095 Montpellier , France .
Abstract:
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.
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