Ponomarenko M. Transannular fluorocyclization of bicyclo[3.3.1]nonane dienes

Transannular cyclization of bicyclo[3.3.1]nonane dienes was accomplished for the first time with electrophilic fluorinating agents F-TEDA-BF4 and (PhSO2)2NF. In protic and nucleophilic solvents, the cyclization is selective and leads to fluorine-containing adamantanes. Based on the reaction of the dienes with N-halosuccinimides in the presence of (C4H9)4N+H2F3- or polyfluorinated alcohols, a convenient preparative approach to 1-fluoro, 1-fluoroalkoxy and 1-polyfluoroalkoxy-3-halogenoalkyladamantanes was developed. By using semiempirical quantum-chemical PM3 calculations, it was shown that the bicyclo[3.3.1]nonane dienes react with N-bromosuccinimide by a trimolecular donor-acceptor mechanism and with F-TEDA-BF4 - via a single electron transfer.