71629-00-0Relevant articles and documents
Stereocontrolled Total Synthesis of (+/-)-Isocomene and (+/-)-β-Isocomene via Ring Enlargement
Tobe, Yoshito,Yamashita, Toshiro,Kakiuchi, Kiyomi,Odaira, Yoshinobu
, p. 898 - 899 (1985)
A total synthesis of (+/-)-isocomene (1) and (+/-)-β-isocomene (2) employing a chelation-controlled regioselective epoxide-carbonyl rearrangement as the key step has been realized.
Stereoselective total synthesis of the sesquiterpene (±)-β- isocomene
Schmidt, Arndt W.,Olpp, Thomas,Baum, Elke,Stiffel, Tina,Kn?lker, Hans-Joachim
, p. 2371 - 2374 (2007)
Application of the Lewis acid mediated [3+2] cycloaddition of allyl-tert-butyldiphenylsilane combined with a modified Fleming-Tamao oxidation provides a stereoselective route to the triquinane sesquiterpene (±)-β-isocomene. Georg Thieme Verlag Stuttgart.
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Wenkert,G.,Arrhenius,T.S.
, p. 2030 (1983)
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Molecular rearrangements of (-)-modhephene and (-)-isocomene to a (-)-triquinane
Joseph-Nathan, Pedro,Reyes-Trejo, Benito,Morales-Rios, Martha S.
, p. 4411 - 4417 (2007/10/03)
The preparation and further rearrangement of (-)-modhephene (1) to a (-)-triquinane 5 has been assessed through acid catalysis. The rearrangement involved protonation, 1,2 σ-bond and methyl shifts, and deprotonation. Monitored experiments by 1H NMR spectroscopy suggested the intermediate (-)-isocomene (3), which was further evidenced when a sample of natural (-)-3 undergoes acid-catalyzed conversion to the (-)-triquinane 5. In addition, deuterated (-)-modhephene (1-d) labeled stereospecifically at the 14β geminal methyl group at C4 was synthesized, through the corresponding chiral deuterated primary alcohol, in 5 steps, starting from natural (-)-14-hydroxymodhephene (8), and rearranged under acid catalysis to elucidate the stereochemical factors that control the methyl shift at this position. The final deuterium-labeled (-)-triquinane, 5-d, obtained from [14- 2H1]-1-d was established to have deuterium in the methyl group at C5 by 13C NMR spectroscopy. This stereoselective methyl migration is in accordance with the molecular orbital demand formulated by the quantum chemical calculations performed in the present study.
Enantio- and diastereocontrolled synthesis of an angular triquinane sesquiterpene (+)-arnicenone.
Iura,Sugahara,Ogasawara
, p. 291 - 293 (2007/10/03)
[figure: see text] (+)-Arnicenone, a sesquiterpene of an angular triquinane isolated from Arnica plants, has been synthesized for the first time in an enantiocontrolled manner from a synthetic equivalent of chiral 2-hydroxymethylcyclopentadienone to deter