Oxygenation of Bicycloheptane and Bicyclooctane with Nitronium Tetrafluoroborate

Article abstract of DOI:10.1021/jo00069a028

Reaction of bicyclo<2.2.1>heptane (1) with nitronium tetrafluoroborate in nitroethane gives bicyclo<2.2.1>heptan-2-one (2).Bicyclo<2.2.1>heptan-2-yl nitrite (3) was observed as the intermediate of the reaction.The reaction of exo-bicyclo<2.2.1>heptan-2-ol (4) with nitrosonium tetrafluoroborate also gave 2.The reaction of 2-norbornyl cation with silver nitrite gave 2.When exo-2-bromobicyclo<2..1>heptane (10) reacted with silver nitrite in ether, 2 and 2-nitrobicyclo<2.2.1>heptan (8) were obtained in 1.3:1 ratio.Reaction of bicyclo<2.2.2>octane (5) with nitronium tetrafluoroborate yields upon aqueous workup bicyclo<2.2.2>octan-1-ol (6).No nitro products were observed in either of the reactions.The mechanism of the observed reactions is discussed.