Novel parallel reaction between a [1,5] sigmatropic alkylthio shift and a [1,5] sigmatropic hydrogen shift observed in a 2H-azepine ring.
Although heating 2-methoxy-2H-azepine results in a [1,5] sigmatropic hydrogen shift, heating 2-propylthio-2H-azepine results in not only a [1,5] sigmatropic hydrogen shift but also a [1,5] sigmatropic propylthio shift. Kinetic measurements reveal that migratory aptitudes increase in the order of MeO < H, PrS. These [1,5] sigmatropic shifts are discussed on the basis of ab initio DFT calculations. [reaction: see text].
Kubota
Yasuhiro
Y
Department of Chemistry, Faculty of Science, Okayama University, Tsushima-Naka 3-1-1, Okayama 700-8530, Japan.
Satake
Kyosuke
K
Okamoto
Hideki
H
Kimura
Masaru
M