TY - JOUR
T1 - A quantitative study on the stereoselectivity of sigmatropic shift reactions in acyclic systems
AU - Castenmiller, W.A.M.
AU - Buck, H.M.
PY - 1979
Y1 - 1979
N2 - The semiempirical MINDO/3 method has been used to study sigmatropic [1,3] shifts in propene, [1,5] shifts in pentadiene and [1,7] shifts in heptatriene, occurring in the suprafacial and antarafacial way. Hydrogen, fluorine and methyl (with retention or inversion of configuration) were taken as the shifting goups. For the [1,3] shifts some STO-3G and 4-31G calculations have also been performed. Good correspondence has been obtained with the stereoselectivity predictions of the Woodward-Hoffmann theory. The activation energy for the allowed reactions is 8–21 lower than the value for the forbidden modes. The shift of a F atom proceeds via an inversion-type mechanism.
AB - The semiempirical MINDO/3 method has been used to study sigmatropic [1,3] shifts in propene, [1,5] shifts in pentadiene and [1,7] shifts in heptatriene, occurring in the suprafacial and antarafacial way. Hydrogen, fluorine and methyl (with retention or inversion of configuration) were taken as the shifting goups. For the [1,3] shifts some STO-3G and 4-31G calculations have also been performed. Good correspondence has been obtained with the stereoselectivity predictions of the Woodward-Hoffmann theory. The activation energy for the allowed reactions is 8–21 lower than the value for the forbidden modes. The shift of a F atom proceeds via an inversion-type mechanism.
U2 - 10.1016/0040-4020(79)80078-2
DO - 10.1016/0040-4020(79)80078-2
M3 - Article
SN - 0040-4020
VL - 35
SP - 397
EP - 407
JO - Tetrahedron
JF - Tetrahedron
IS - 3
ER -