Electron-transfer Photochemistry of Endoperoxides

Article abstract of DOI:10.1016/0022-328X(93)80433-C

Derivatives of 1,2-dioxacyclohex-4-ene and 2,3-dioxabicyclo<2.2.2>oct-5-ene (endoperoxides, EPs) form EDA complexes with tetracyanoethylene (TCNE).The phenyl-substituted EPs 3a, 4a, 4b and 6 undergo electron-transfer-induced reactions when the EDA complexes are irradiated.Two types of reactions are observed depending on the ring system.Monocyclic EPs (3a, 4a and 4b) afford furan derivatives, possibly through the Criegee-type rearrangement, and dehydration, whereas the bicyclic EP 6 undergoes cycloreversion through the C-O bond cleavage.