136458-41-8Relevant academic research and scientific papers
The synthesis of mono- and dihydroxy aromadendrane sesquiterpenes, starting from natural (+)-aromadendrene-III
Gijsen, Harrie J. M.,Wijnberg, Joannes B. P. A.,Stork, Gerrit A.,De Groot, Aede,De Waard, Maarten A.,Van Nistelrooy, Johannes G. M.
, p. 2465 - 2476 (2007/10/02)
The monoalcohols (-)-globulol (2), (-)-epiglobulol (3), (-)-ledol (4), and (+)-viridiflorol (5) were synthesized from (+)-aromadendrene (1). The cis-fused alloaromandedrone (14), the key intermediate used in the synthesis of 4 and 5, was obtained from the trans-fused apoaromadendrone (13) via a selective protonation of the thermodynamic enol trimethylsilylether 15. After hydroxylation of the tertiary C11 of 13 with RuO4, (+)-spathulenol (6), (-)-allospathulenol (7), and the aromadendrane diols 8-11 could be prepared. Compounds 2-11 were tested for antifungal properties, but their activity was only moderate.
Base-Induced and -Directed Elimination and Rearrangement of Perhydronaphthalene-1,4-diol Monosulfonate Esters. Total Synthesis of (+/-)-Alloaromadendrane-4β,10α-diol and (+/-)-Alloaromadendrane-4α,10α-diol
Jenniskens, Louis H. D.,Wijnberg, Joannes B. P. A.,Groot, Aede de
, p. 6585 - 6591 (2007/10/02)
The total synthesis of (+/-)-alloaromadendrane-4β,10α-diol (1), supposedly isolated from Ambrosia peruviana Willd., is described.The strategically positioned axial hydroxyl group at C(4) played a crucial role in the two key steps of this synthesis (2 and 11 -> 3; 4 -> 5).Upon treatment with sodium tert-amylate in refluxing toluene, both the mesylates 2 and 11 predominantly gave the olefin 3.A mechanism for this regioselective elimination is proposed.The double bond of 3 at C(6)-C(7) was used to introduce a dimethylcyclopropane ring at this position.The intramolecular base-induced rearrangement of 4 proceeded with high selectivity, again guided by the alkoxide at C(4).The resulting exo olefin 5 was converted into diol 1, but its spectral data did not agree with those reported for the natural diol.The epimeric (+/-)-alloaromadendrane-4α,10α-diol (23) was prepared from 5 via a dehydratation, epoxidation, reduction sequence.Now the spectral data of the natural and the synthetic diol agreed very well and a revision of the structure of the natural product is postulated.
FOUR HELIANGOLIDES AND OTHER SESQUITERPENES FROM BRASILIA SICKII
Bohlmann, Ferdinand,Grenz, Michael,Jakupovic, Jasmin,King, Robert M.,Robinson, Harold
, p. 1213 - 1218 (2007/10/02)
The investigation of Brasilia sickii afforded, in addition to known compounds, two new bisabolene derivatives, an acetate closely related to damsinic acid together with its methyl ester, a dihydroxyaromadendrane, a thymol derivative and four heliangolides, closely related to a similar lactone isolated from a Calea species.The structures were elucidated by high field 1H NMR spectroscopy and a few chemical transformations, while the sructure of the spathulenol derivative was established by partial synthesis.The chemotaxonomy is discussed briefly. - Key Word Index: Brasilia sickii; Compositae; sesquiterpene lactones; heliangolides; sesquiterpenes; bisabolene derivatives; damsinic acid derivative; spathulenol derivative; thymol derivative; triterpene isovalerate.
