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DOI: 10.1055/s-0030-1258412
Total Syntheses of (±)-(Z)- and (±)-(E)-9-(Bromomethylene)-1,5,5-trimethylspiro[5.5]undeca-1,7-dien-3-one and (±)-Majusculone
Publikationsverlauf
Publikationsdatum:
18. Januar 2011 (online)
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Abstract
A new total synthesis of the chamigrene sesquiterpenoids (Z)-9-(bromomethylene)-1,5,5-trimethylspiro[5.5]undeca-1,7-diene-3-one and its 15-E-epimer has been accomplished in 13 steps. In our sequence, a Diels-Alder reaction and subsequent reductive alkylation of the resulting adduct was utilized as the key strategy to create the A-ring and the quaternary spirocenter with the suitable functionalities for accessing the B-ring. Additionally, from the advanced intermediate, a total synthesis of (±)-majusculone, a nor-chamigrene natural product, was also readily achieved in two steps.
Key words
chamigrenes - sesquiterpenes - majusculone - total syntheses - Diels-Alder reaction
- Supporting Information for this article is available online:
- Supporting Information
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To resolve the stereochemistry of 11, we further converted it into (3S*,5S*)-3,5-dimethyl-4-acetylcyclohexanone by treating with TBAF in THF. Given with the fixed trans relationship between the C-4 acetyl and C-3 methyl groups, the relative steric relationships between the C-5 methyl and the C-4 acetyl groups could be deduced from the coupling constants of C-4 methine proton at δ = 2.72 (dd, J = 9.1, 3.7 Hz) from the ¹H NMR spectrum (see Supporting Information).