title: Solvolysis of (4,5)-anti-4-aryl-5-tosyloxy-2(E)-hexenoate derivatives.
abstract: 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.
authors.affiliation: School of Pharmaceutical Sciences, Toho University, Chiba, Japan.
authors.forename: Machiko
authors.initials: M
authors.lastname: Ono
authors.forename: Takeru
authors.initials: T
authors.lastname: Ehara
authors.forename: Hirofumi
authors.initials: H
authors.lastname: Yokoyama
authors.forename: Nobuyoshi
authors.initials: N
authors.lastname: Ohtani
authors.forename: Youko
authors.initials: Y
authors.lastname: Hoshino
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Akita
mesh_terms: D002208:Caproates / Q000138:chemical synthesis* / Q000737:chemistry; D006868:Hydrolysis; D008968:Molecular Conformation; D013237:Stereoisomerism
chemical_list: D002208:Caproates