Modulating Electrostatic Interactions in Ion Pair Intermediates To Alter Site Selectivity in the C−O Deoxygenation of Sugars

Controlling which products one can access from the predefined biomass‐derived sugars is challenging. Changing from CH₂Cl₂ to the greener alternative toluene alters which C?O bonds in a sugar are cleaved by the tris(pentafluorophenyl)borane/HSiR₃ catalyst system. This increases the diversity of high‐value products that can be obtained through one‐step, high‐yielding, catalytic transformations of the mono‐, di‐, and oligosaccharides. Computational methods helped identify this non‐intuitive outcome in low dielectric solvents to non‐isotropic electrostatic enhancements in the key ion pair intermediates, which influence the reaction coordinate in the reactivity‐/selectivity‐determining step. Molecular‐level models for these effects have far‐reaching consequences in stereoselective ion pair catalysis.