Facile Reduction of 1,2‐Dioxetanes by Thiols as Potential Protective Measure against Photochemical Damage of Cellular DNA

Vicinal diols and disulfides are the products of the title reaction, which presumably is initiated by a one-electron transfer according to (a) (XH). The oxygen transfer in the reaction of dioxetanes and sulfides (XR″) as well as the cleavage of a dioxetane molecule into two ketone molecules, observed in both cases as a side reaction, can also be explained in terms of starting from the radical ion pair in (a). The first experimental proof has been found for the reduction of dioxetanes by glutathione in biological systems actually being decisive for their conversion into non-toxic compounds.