Reactions of quadricyclane with fluorinated nitrogen-containing compounds.: Synthesis of 3-aza-4-perfluoroalkyl-tricyclo [4.2.1.02,5]non-3,7-dienes

The cycloaddition reactions of quadricyclane (1) and polyfluorinated imines and nitriles were studied. Both (CF3)(2)C=NH and (CF3)(2)C=N-(2-F-C6H4) were found to have low reactivity towards 1, giving the corresponding [2 + 2 + 2] cycloadducts in a low yield. C2F5N=CFCF3 however, reacts with 1 rapidly, giving a mixture of two isomeric cycloadducts in a high yield. Perfluoroalkyl nitriles RfCN (R-f = CF3, C2F5, n-C3F7) were found to have surprisingly high reactivity to 1 producing exo-3-aza-4-(fluoroalkyl)-tricyclo[4.2.1.0(2.5)]non-3,7-dienes in 56-81% yields at elevated temperature. Exo-3-aza-4-(perfluoroalkyl)-tricyclo[4.2.1.0(2.5)]non-3,7-dienes rapidly react with CF3Si(CH3)(3) in the presence of CsF catalyst. The reaction results in addition of CF3Si(CH3)(3) across the C=N bond of the azadienes with selective formation of only one stereoisorner of exo-3-aza-3-(trimethylsilyl)-4,4-bis(perfluoroalkyl)-tricyclo[4.2.1.0(2.5)]non-7-enes. Silyl group in this compounds can be removed either by the action of tetrabutyl ammonium fluoride hydrate, leading to the formation of the corresponding amine after hydrolysis, or by reaction with HCl resulting in the formation of the corresponding amine hydrochloride. (C) 2004 Elsevier B.V. All rights reserved.