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).
[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.
Di Stefano
Stefano
S
Istituto di Chimica Biomolecolare del CNR, Sezione di Roma, Dipartimento di Chimica, Ingegneria Chimica e Materiali, Università degli Studi de L'Aquila, Rome, Italy.
Leonelli
Francesca
F
Garofalo
Barbara
B
Mandolini
Luigi
L
Marini Bettolo
Rinaldo
R
Migneco
Luisa Maria
LM