A Change from Kinetic to Thermodynamic Control Enables trans-Selective Stereochemical Editing of Vicinal Diols

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.

Automated summary

This report describes a new method for the selective catalytic isomerization of cis-1,2-diols using a silanethiol catalyst. The method is highly chemoselective and tolerant to a wide range of functional groups, providing a concise route to trans-diol products. Mechanistic studies suggest that the isomerization proceeds through a reversible hydrogen atom transfer pathway mediated by the silanethiol catalyst.