Novel Rearrangement of an Isocaryolane Sesquiterpenoid under Mitsunobu Conditions

• Published in: Journal of organic chemistry Vol. 65; no. 23; pp. 7786 - 7791
• Main Authors: Racero, Juan C, Macías-Sánchez, Antonio J, Hernández-Galán, Rosario, Hitchcock, Peter B, Hanson, James R, Collado, Isidro G
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 17.11.2000; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; BOTRYTIS-CINEREA; TETRACYANOETHYLENE
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo000765p

Under modified Mitsunobu reaction conditions, a novel skeleton rearrangement of terpenes has been obtained. The reactivity of 8,9-dioxygenated isocaryolane derivatives has been investigated. When either (8R,9R)-8-methoxyisocaryolane-9-ol (7) or (8R,9R)-isocaryolane-8,9-diol (10) are treated under acidic conditions, isocaryolan-9-one (9) and the rearrangement compound (1S,2S,5R,8S)-1,4,4-trimethyltricyclo[6.2.1.02,5]undecane-8-carbaldehyde (11) are obtained. Otherwise treatment of compounds 7 and 10 under modified Mitsunobu conditions leads to the novel sesquiterpene derivative (1S,2S,5R,9R)-1,4,4-trimethyltricyclo[7.2.1.02,5]dodecan-8-one (8). This is the first example, to our knowledge, of a Mitsunobu-induced pinacol rearrangement. The influences of the substrate and reaction conditions on the evolution of the reaction are both explored. This modification of the Mitsunobu reaction conditions introduces a new, one-pot, procedure for preparing this class of rearrangement product.