Oxygen-to-Oxygen Silyl Migration of α-Siloxy Sulfoxides and Oxidation-Triggered Allicin Formation.

Oxidation of α-siloxy thioethers leads to the formation of the corresponding sulfoxides as unstable intermediates, which undergo an intramolecular oxygen-to-oxygen silyl migration to break the C-S linkage. This process produces silyl protected sulfenic acids and subsequently thiosulfinates. It was used to develop oxidation-triggered allicin donors.