Bk. Carpenter, DYNAMIC MATCHING - THE CAUSE OF INVERSION OF CONFIGURATION IN THE [1,3] SIGMATROPIC MIGRATION, Journal of the American Chemical Society, 117(23), 1995, pp. 6336-6344
Direct dynamics calculations using the PM3 semiempirical molecular orb
ital method are carried out on the formal [1,3] sigmatropic migration
that interconverts bicyclo[3.2.0]hept-2-ene and norbornene. Methylated
analogs are also investigated. It is shown that, despite the existenc
e of a 5 kcal/mol local minimum corresponding to a biradical intermedi
ate on the PM3 potential energy surface for the reaction, the transfor
mation still occurs with a preference for inversion of configuration a
t the migrating carbon. This stereoselectivity is dynamic in origin an
d has nothing to do with conservation of orbital symmetry. It can be o
vercome with a suitably placed methyl substituent. asis observed exper
imentally. The calculations result in movies that the reader can find
on the World Wide Web ttp://www.chem.cornell.edu/bkc1/Sigmatrophy.html
). The implications of the calculations for the mechanisms of nominal
[1,n] sigmatropic shifts of carbon are discussed.