Use of Constrained G‐Quadruplexes for Enantioselective Sulfoxidation Site Mapping

Abstract

AbstractCatalysis 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, G‐4 was chemically constrained into a unique topology. It was shown 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. By means of these G‐4 mimics, the enantioselective control of the sulfoxidation reaction was unraveled.