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 CH3ONa/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-ondo-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.
Elusive 6-exo-Hydroxybicyclo[2.2.2]octan-2-ones from the Corresponding Acetates by Methanolysis in the Presence of CH3ONa/La(OTf)3 / DI STEFANO, Stefano; Leonelli, Francesca; Garofalo, B; Mandolini, Luigi; MARINI BETTOLO, Rinaldo; Migneco, Luisa Maria. - In: ORGANIC LETTERS. - ISSN 1523-7060. - STAMPA. - 4:(2002), pp. 2783-2785. [10.1021/ol026326p]
Elusive 6-exo-Hydroxybicyclo[2.2.2]octan-2-ones from the Corresponding Acetates by Methanolysis in the Presence of CH3ONa/La(OTf)3
DI STEFANO, Stefano;LEONELLI, Francesca;MANDOLINI, Luigi;MARINI BETTOLO, Rinaldo;MIGNECO, Luisa Maria
2002
Abstract
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 CH3ONa/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-ondo-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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
