A rational quest for selectivity through precise ligand-positioning in tandem DNA-catalysed Friedel–Crafts alkylation/asymmetric protonation

Justine Mansot (1) , Sidonie Aubert (2) , Nicolas Duchemin (2) , Jean-Jacques Vasseur (1) , Stellios Arseniyadis (2) , Michael Smietana (1)

1 IBMM - Institut des Biomolécules Max Mousseron [Pôle Chimie Balard]
2 QMUL - Queen Mary University of London

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.

Mots clés: OLIGONUCLEOTIDES; RNA; BUILDING-BLOCKS; DUPLEX STABILITY; ENANTIOSELECTIVE PROTONATION; ASYMMETRIC CATALYSIS; SITE; PROTEIN

Domaines: Chimie; Chimie organique; Chimie analytique; Catalyse

Justine Mansot, Sidonie Aubert, Nicolas Duchemin, Jean-Jacques Vasseur, Stellios Arseniyadis, et al.. A rational quest for selectivity through precise ligand-positioning in tandem DNA-catalysed Friedel–Crafts alkylation/asymmetric protonation. Chemical Science, 2019, 10 (10), pp.2875-2881. ⟨10.1039/c8sc05543b⟩. ⟨hal-02197146⟩