title: Elusive 6-exo-Hydroxybicyclo[2.2.2]octan-2-ones from the corresponding acetates by methanolysis in the presence of CH(3)ONa/La(OTf)(3).
abstract: [reaction: see text] A series of 6-exo-acetoxybicyclo[2.2.2]octan-2-ones were converted into the corresponding 6-exo-hydroxybicyclo[2.2.2]octan-2-ones by methanolysis in the presence of CH(3)ONa/La(OTf)(3). Under the given conditions, epimerization at C(6) of the latter led in the least favorable cases only to traces of the more stable 6-endo-hydroxybicyclo[2.2.2]octan-2-ones. This procedure, when combined with the described conversion of easily available 6-endo-hydroxybicyclo[2.2.2]octan-2-ones into the corresponding 6-exo-acetoxy derivatives, provides a convenient route to elusive 6-exo-hydroxybicyclo[2.2.2]octan-2-ones. Applications to total synthesis are shown and envisaged.
authors.affiliation: Istituto di Chimica Biomolecolare del CNR, Sezione di Roma, Dipartimento di Chimica, Ingegneria Chimica e Materiali, Università degli Studi de L'Aquila, Rome, Italy.
authors.forename: Stefano
authors.initials: S
authors.lastname: Di Stefano
authors.forename: Francesca
authors.initials: F
authors.lastname: Leonelli
authors.forename: Barbara
authors.initials: B
authors.lastname: Garofalo
authors.forename: Luigi
authors.initials: L
authors.lastname: Mandolini
authors.forename: Rinaldo
authors.initials: R
authors.lastname: Marini Bettolo
authors.forename: Luisa Maria
authors.initials: LM
authors.lastname: Migneco