Collect. Czech. Chem. Commun. 2002, 67, 1517-1532

[3,3] Sigmatropic Rearrangement of Some Fluorinated 1,5-Hexadienes

William R. Dolbier, Jr.a, Keith W. Palmera, Feng Tiana, Piotr Fiedorowb, Andrzej Zaganiaczykb and Henryk Koroniakb,*

a University of Florida, Department of Chemistry, Gainesville, FL 32611, U.S.A.
b Adam Mickiewicz University, Faculty of Chemistry, Grunwaldzka 6, 60-780 Poznań, Poland


Fluorine atoms incorporated into 1,5-hexadiene molecule should influence the kinetic as well as the thermodynamic parameters of [3,3] sigmatropic rearrangement (Cope rearrangement). Within few decades is has been documented that this transformation proceeds in a concerted manner, rather than stepwise with some radical intermediates involved. Few new terminally fluorinated 1,5-hexadienes (compounds 3, 5A, 7, 9 and 5B) have been synthesized. The activation parameters of rearrangement have been determined and compared with those known for hydrocarbon analogues. While systems developing chair-like transition states (compounds 3 and 5) showed close similarity with hydrocarbon analogues (compound 1), those developing boat-like transition states (compounds 7, 9 and 5B) may proceed through radical stepwise mechanism. Computational studies of the transition states were carried out, showing that only ab initio methods (MP2 and especially DFT) can give approximate correlation with experimental data, whereas in the case of hydrocarbon analogues even simple semiempirical methods (AM1) were reliable enough to reproduce experimental results.

Keywords: Sigmatropic rearrangements; Cope rearrangement; Dienes; Fluorinated compounds; Transition states; Ab initio calculations; Conformation analysis.

References: 24 live references.