82467-48-9Relevant articles and documents
Stereospecific Rearrangements in Tricyclopentanoid Sesquiterpenes: The Absolute Configuration of (-)-Isocomene, (-)-β-Isocomene, and (-)-Silphinene
Fitjer, Lutz,Monzo-Oltra, Honorato
, p. 6171 - 6173 (1993)
The determination of the absolute configuration of (-)-isocomene ((-)-9), (-)-β-isocomene ((-)-3), and (-)-silphinene ((-)-15) by correlation with (-)-modhephene ((-)-(3aR,4R,6aS)-4) via stereospecific rearrangements is described.
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.
Sesquiterpene constituents in Petasites hybridus
Saritas, Yücel,Von Reu, Stephan H.,K?nig, Wilfried A.
, p. 795 - 803 (2007/10/03)
The essential oil of the rhizomes of Petasites hybridus (Asteraceae) was investigated by gas chromatography, mass spectrometry, 1- and 2-dimensional NMR techniques and chemical correlations. Two new sesquiterpene hydrocarbons, petasitene and pethybrene, c
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
General Methodology for the Topologically Selective Preparation of Linear and Nonlinear Tricyclopentanoids of Hirsutane and Isocomene Type via a Claisen Rearrangement/Cyclopentene Annulation Sequence. Total Synthesis of (+/-)-Epiisocomene
Hudlicky, Tomas,Kwart, Lawrence D.,Tiedje, Mark H.,Ranu, Brindaban C.,Short, Robert P.,et al.
, p. 716 - 727 (2007/10/02)
The intramolecular cyclopentene annulation methodology which combines the cyclopropanation of dienic diazoketones and the vinylcyclopropane rearrangement is utilized to synthesize linear tricyclopentanoids of the hirsutane class or nonlinear members of the isocomene class.The requisite diene precursors, endocyclic or exocyclic, respectively, are obtained from acylcyclopentenes via orthoester Claisen rearrangement of either allyl or propargyl alcohols.The scope and the generality of the method are indicated and experimental details are presented pertaining to thesynthesis of precursory dienes for hirsutane and isocomene sesquiterpenes.Full details are disclosed concerning the total synthesis of epiisocomene and the synthesis of linearly fused precursors to coriolin sesquiterpenes.
PHLOROGLUCINOL DERIVATIVES AND OTHER CONSTITUENTS FROM SOUTH AFRICAN HELICHRYSUM SPECIES
Jakupovic, J.,Kuhnke, J.,Schuster, A.,Metwally, M. A.,Bohlmann, F.
, p. 1133 - 1142 (2007/10/02)
Key Word Index - Helichrysum species; Compositae; phloroglucinol derivatives; chromanes; benzofuranes; α-pyrone derivatives; diterpenes; geranyl linalol derivatives; isocomene derivative. The investigation of 11 South African Helichrysum species afforded in addition to known compounds 26 further phloroglucinol derivatives, nine diterpenes, a derivative of isocomene and an α-pyrone derivative.The structures were elucidated by highfield NMR spectroscopy and a few chemical transformations.Furthermore the structures of several phloroglucinol derivatives were established by synthesis.The chemotaxonomy is discussed.
STEREOCONTROLLED TOTAL SYNTHESIS OF ISOCOMENE SESQUITERPENES
Ranu, Brindaban C.,Kavka, Misha,Higgs, Leslie A.,Hudlicky, Tomas
, p. 2447 - 2450 (2007/10/02)
Four isomers of the sesquiterpene isocumene have been synthesized in high yields and in a stereocontrolled fashion from the tricyclic triquinane 1 obtained by the cyclopentene annulation method.Carbon-13 data was obtained for all the isocomene sesquiterpe
A total synthesis of (±)-isocomene and (±) β-isocomene by an intramolecular ene reaction
Oppolzer,Bttig,Hudlicky
, p. 4359 - 4364 (2015/01/08)
The racemic sesquiterpenes isocomene I and β-isocomene 22 have been synthesized starting from l,7-octadien-3-one (0 in a stereoselective manner. In the key step 12 →13 (Scheme 5) the C-7, C-8-bond was formed by an intramolecular thermal ene reaction. Furt
SESQUITERPENE HYDROCARBONS FROM THE ROOTS OF OTANTHUS MARITIMUS
Teresa, J. de Pascual,Feliciano, A. San,Barrero, A. F.,Medarde, M.,Tome, F.
, p. 166 - 167 (2007/10/02)
Key Word Index - Otanthus maritimus; Anthemideae; Compositae; sesquiterpenes.
