Torsional strain inversed chemoselectivity in a Pd-catalyzed atroposelective carbonylation reaction of dibenzothiophenium
Qiu‐Chi Zhang, Xiaoping Xue, Biqiong Hong, Zhenhua Gu
Abstract
A palladium-catalyzed enantioselective ring-opening/carbonylation of cyclic diarylsulfonium salts is reported. In comparison to thioethers, the sulfonium salts displayed high reactivity and enabled the reaction to be performed under mild conditions (room temperature). The steric repulsion of the two non-hydrogen substituents adjacent to the axis led cyclic diarylsulfonium salts to be distorted, which enabled the ring-opening reaction to proceed with significant preference for breaking the exocyclic C-S bond.
Topics & Concepts
ChemoselectivityChemistryCarbonylationSulfoniumCatalysisEnantioselective synthesisSteric effectsRing (chemistry)Reactivity (psychology)Medicinal chemistryRing strainPalladiumStereochemistryOrganic chemistryCarbon monoxideMedicinePathologyAlternative medicineSalt (chemistry)Axial and Atropisomeric Chirality SynthesisMolecular spectroscopy and chiralityAsymmetric Synthesis and Catalysis