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)

Stefano Di Stefano; Francesca Leonelli; Barbara Garofalo; Luigi Mandolini; Rinaldo Marini Bettolo; Luisa Maria Migneco

doi:10.1021/ol026326p

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)

Org Lett. 2002 Aug 8;4(16):2783-5. doi: 10.1021/ol026326p.

Authors

Stefano Di Stefano¹, Francesca Leonelli, Barbara Garofalo, Luigi Mandolini, Rinaldo Marini Bettolo, Luisa Maria Migneco

Affiliation

¹ Istituto di Chimica Biomolecolare del CNR, Sezione di Roma, Dipartimento di Chimica, Ingegneria Chimica e Materiali, Università degli Studi de L'Aquila, Rome, Italy.

PMID: 12153234
DOI: 10.1021/ol026326p

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.