A Change from Kinetic to Thermodynamic Control Enables <i>trans-</i>Selective Stereochemical Editing of Vicinal Diols
Yu‐An Zhang, Xin Gu, Alison E. Wendlandt
Abstract
Here, we report the selective, catalytic isomerization of cis-1,2-diols to trans-diequatorial-1,2-diols. The method employs triphenylsilanethiol (Ph3SiSH) as a catalyst and proceeds under mild conditions in the presence of a photoredox catalyst and under blue light irradiation. The method is highly chemoselective, broadly functional group tolerant and provides concise access to trans-diol products which are not readily obtained using other methods. Mechanistic studies reveal that isomerization proceeds through a reversible hydrogen atom transfer pathway mediated by the silanethiol catalyst.
Topics & Concepts
ChemistryIsomerizationVicinalCatalysisDiolHydrogen atomPhotoisomerizationPhotochemistryKinetic controlCombinatorial chemistryOrganic chemistryGroup (periodic table)Radical Photochemical ReactionsAsymmetric Synthesis and CatalysisChemical Synthesis and Analysis