Solvolysis of (4,5)-anti-4-aryl-5-tosyloxy-2(E)-hexenoate derivatives.
The solvolysis reaction of (4,5)-anti-4-aryl-5-tosyloxy-2(E)-hexenoates 4a-k gave (4,5)-anti-4-aryl-5-hydroxy-2(E)-hexenoates 2a-k and (4,5)-anti-5-aryl-4-hydroxy-2(E)-hexenoates 5a-k along with the complete inversion. This 1,2-aryl migration was induced by treatment with heating in water-saturated nitromethane. On the basis of the substituent effect on the aromatic ring, this 1,2-aryl migration is thought to proceed via the sigma-bridged phenonium ion. The product selectivity between 2a-k and 5a-k was found to be subtly governed by the substituent and substitution pattern in the aromatic ring of the substrates 4a-k.
Ono
Machiko
M
School of Pharmaceutical Sciences, Toho University, Chiba, Japan.
Ehara
Takeru
T
Yokoyama
Hirofumi
H
Ohtani
Nobuyoshi
N
Hoshino
Youko
Y
Akita
Hiroyuki
H
D002208:Caproates / Q000138:chemical synthesis* / Q000737:chemistry; D006868:Hydrolysis; D008968:Molecular Conformation; D013237:Stereoisomerism
D002208:Caproates