Use of Constrained G‐Quadruplexes for Enantioselective Sulfoxidation Site Mapping

Abstract

Catalysis using G‐quadruplexes (G‐4) has shown promise as a way to perform asymmetric sulfoxidation of thioanisole derivatives. However, despite the relative simplicity of G‐4, the mechanism of chiral control of sulfoxidation is still unknown, mainly because G‐4 can adopt different topologies. To better understand the mechanism of G‐4‐catalyzed sulfoxidation, we chemically constrained G‐4 into a unique topology. We show that either sulfoxidation can occur at the outer tetrads or at the grooves of G‐4 and that different enantiomers can be generated depending on the region where catalysis occurs. Thus, thanks to our G‐4 mimics, we can unravel the enantioselective control of the sulfoxidation reaction.