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Novel Rearrangement of an Isocaryolane Sesquiterpenoid under Mitsunobu Conditions

journal contribution
posted on 2023-06-07, 22:13 authored by Juan C Racero, Antonio J Macias-Sanchez, Rosario Hernandez-Galan, Peter B Hitchcock, James R Hanson, Isidro G Collado
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.

History

Publication status

  • Published

Journal

Journal of Organic Chemistry

Publisher

Journal of Organic Chemistry

Volume

65

Page range

7786 - 7791

ISBN

0022-3263

Department affiliated with

  • Chemistry Publications

Full text available

  • No

Peer reviewed?

  • Yes

Legacy Posted Date

2012-02-06

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