Skeletal rearrangement of a 2,6-dithiaadamantane-2,2,6,6-tetraoxide derivative during thermal and photochemical sulfur dioxide extrusion.

In contrast to the pyrolysis of 1 which results in loss of both SO₂ groups and formation of 4, the photolysis of 1 results in loss of only one SO₂ group, a double 1,3-shift of the second sulfonyl group and formation of 3. Pyrolysis of the latter also gives 4. The mechanistic significance and novelty of these results are discussed.