Molybdenum-Catalyzed Enantioselective Sulfoxidation Controlled by a Nonclassical Hydrogen Bond between Coordinated Chiral Imidazolium-Based Dicarboxylate and Peroxido Ligands.

ABSTRACT: Chiral alkyl aryl sulfoxides were obtained by molybdenum-catalyzed oxidation of alkyl aryl sulfides with hydrogen peroxide as oxidant in mild conditions with high yields and moderate enantioselectivities. The asymmetry is generated by the use of imidazolium-based dicarboxylic compounds, HLR. The in-situ-generated catalyst, a mixture of aqueous [Mo(O)(O₂)₂(H₂O)n] with HLR as chirality inductors, in the presence of [PPh₄]Br, was identified as the anionic binuclear complex [PPh₄]{[Mo(O)(O₂)₂(H₂O)]₂(μ-LR)}, according to spectroscopic data and Density Functional Theory (DFT) calculations. A nonclassical hydrogen bond between one C⁻H bond of the alkyl R group of coordinated (LR)− and one oxygen atom of the peroxido ligand was identified as the interaction responsible for the asymmetry in the pro

SUBMITTER: Carrasco CJ 

PROVIDER: S-EPMC6100257 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature