Electron-transfer Reactions of Bicyclic Systems

Electron-transfer Reactions of Bicyclic Systems 107 Bicydopentane radical cation... 

Bicyclic ring systems containing three or four-membered rings have special bonding forces, which are reflected in their unusual chemistry. Their electron-transfer reactions have been studied in the gas, liquid, and solid phases, and the structure and reactivity of their radical cations have been the target of intense scrutiny. 

Intramolecular electron transfer initiated cyclization reaction of 7V-allyliminium salt systems may also generate 3-pyrrolidinyl ethers or alcohols in monocyclic and bridged or fused bicyclic systems (e.g. equations 63 - 65)122,123. 

The photochemical reactions of the bicyclic compounds (201 a, c) in acetonitrile-methanol solution in the presence of 1,4-dicyanobenzene have been studied. The irradiation of (201a) affords the mixture of trans cis methoxy derivatives (201b) which are also photochemically reactive under the same conditions. The products from (201a) are formed by the photochemical addition of methanol to the furan (202). This furan is formed by production of the radical cation of (201a) followed by deprotonation affording a doubly benzylic radical. The study was extended to the monocyclic system (203) which on electron-transfer-induced irradiation afforded the acetal... 

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