An easy procedure to obtain extracts enriched in trixagol monomalonylesther (1) from aerial parts of the plant Belladia trixago chemotype Trix was developed. Preparation of (+)-dihydro-γ-ionone (4) was carried out directly from the extracts with good yields by selective oxidation. Other interesting odorant products as α-ambrinol (5), ambraldehyde (6) and the tricyclic compound 7 were synthesized very efficiently using (4) as intermediate.
ErsozT., YalcinF.N., TasdemirD., SticherO., CalisI. (1998) Iridoid and lignan glucosides from Bellardia trixago (L.) All. Turkish Journal of Medicinal Science, 28, 397–400.
2.
Tomas-BarberanF.A., ColeM.D., Garcia-VigueraC., Tomas-LorenteF., GuiradoA. (1990) Epicuticular flavonoids from Bellardia trixago and their antifungal fully methylated derivatives. International Journal of Crude Drug Research, 28, 57–60.
3.
(a) De Pascual TeresaJ., CaballeroE., CaballeroC., MedardeM., BarreroA.F., GrandeM. (1978) Trixagol, natural γ-cyclogeranyl-geraniol from Bellardia trixago (L.) All. Tetrahedron Letters, 19, 3491–3494. (b) De Pascual Teresa J, Caballero E, Caballero C, Medarde M, Barrero AF, Grande M. (1982) Minor components with the γ-cyclogeranil geraniol skeleton from Bellardia trixago (L.) All. Tetrahedron, 38, 1837-1842.
4.
BarreroA.F., SánchezJ.F., CuencaF.G. (1988) Dramatic variation in diterpenoids of different populations of Bellardia trixago. Phytochemistry, 27, 3676–3678.
5.
ParraA., LópezP.E., Garcia-GranadosA. (2010) Bioactive compounds with added value prepared from terpenes contained in soil vastes from the olive oil industry. Chemistry and Biodiversity, 7, 421–439.
6.
(a) RuzickaL., SeidelC.F., PfeifferM. (1948) The volatile components of ambergris. I. Isolation of dihydro-γ-ionone. Helvetica Chimica Acta, 31, 827–831;(b) Kawanobe T, Kogami K, Hayashi K, Matsui M. (1984) New synthesis of γ-homocyclogeranial, γ-dihydroionone and their derivatives. Agricultural and Biological Chemistry, 48, 461-464.
7.
TheimerET. Ed. (1982) Fragrance Chemistry. The Science of the Sense of Smell”.Academic Press.New York, pg. 540 and references herein cited.
8.
ShenY.C., ChengS.Y., KuoY.H., HwangT.L., ChiangM.Y., KhalilT. (2007) Chemical transformation and biological activities of ambrein, a major product of ambergris from Physeter macrocephalus (sperm whale). Journal of Natural Products, 70, 147–153.
9.
(a) StollM. (1955) Odor and constitution. XIV. New method of preparation of dihydro-γ-ionone. Helvetica Chimica Acta, 38, 1587–1593;(b) Serra S, Fuganti C, Brenna E. (2007) Two easy photochemical methods for the conversion of commercial ionone alpha into regioisomerically enriched γ-ionone and γ-dihydroionone. Flavour and Fragrance Journal, 22, 505-511. (c) Fuganti C, Serra S, Zenomi A. (2000) Synthesis and olfactory evaluation of (+)- and (-)-γ-ionone. Helvetica Chimica Acta, 83, 2761-2768; (d) Engler TA, Ali MH, Takusagawa F. (1996) Studies on the Synthesis of Acanthodoral and Nanaimoal: Evaluation of Cationic Cyclization Routes. Journal of Organic Chemistry, 61, 8456-8463; (e) Magatti CV, Kaminski JJ, Rothberg I. (1991) Total synthesis of dehydroambliol-A and its unnatural Z isomer. Journal of Organic Chemistry, 56, 3102-3106. (f) Barrero AF, Alvarez-Manzaneda EJ, Chahboun R, Cuerva JM, Segovia A. (2000) Synthetic applications of the thermal rearrangement of ozonides: first enantiospecific synthesis of marine metabolite luffarin W. Synlett, 1269-1272. (g) Fujiwara N, Kinoshita M, Akita H. (2006) New total synthesis of (+)-ambrein. Tetrahedron: Asymmetry, 17, 3037-3045; (h) Justicia J, Campaña AG, Bazdi B, Robles R, Cuerva JM, Oltra E. (2008) Titanium-catalized enantioselective synthesis of α-ambrinol. Advaced Synthesis & Catalysis, 350, 751-757.
10.
(a) BarreroA.F., HerradorM.M., ArteagaP., CatalanJ.V. (2009) Ilicic Acid as a natural chiron for the efficient preparation of bioactive α- and β-eudesmol. European Journal of Organic Chemistry, 3589–3594; (b) Alvarez-Manzaneda EJ, Romera JL, Barrero AF, Alvarez-Manzaneda R, Chahboun R, Meneses R, Aparicio M. (2005) Synthetic approach to pentacyclic quassinoids from communic acids, via ambracetal derivatives. Tetrahedron, 61, 837-844; (c) Barrero AF, Alvarez-Manzaneda EJ, Chahboun R, Arteaga AF. (2004) Degradation of the side chain of (-)-sclareol: A very short synthesis of nor-ambreinolide and ambrox. Synthetic Communications, 34, 3631-3643; (d) Barrero AF, Alvarez-Manzaneda EJ, Alvarez-Manzaneda R, Chahboun R, Meneses R, Cuerva JM, Aparicio M, Romera JL. (2001) Approach to the synthesis of antitumor quassinoids from labdane diterpenes: An efficient synthesis of a picrasane-related intermediate. Organic Letters, 3, 647-650; (e) Barrero AF, Arseniyadis S, Quilez del Moral JF, Herrador MM, Valdivia M, Jimenez D. (2002) First synthesis of the antifungal oidiolactone C from trans-communic acid: cytotoxic and antimicrobial activity in podolactone-related compounds. Journal of Organic Chemistry, 67, 2501-2508; (f) Barrero AF, Alvarez-Manzaneda EJ, Herrador MM, Chahboun R, Galera P. (1999) Synthesis and antitumoral activities of marine ent-chromazonarol and related compounds. Bioorganic and Medicinal Chemistry Letters, 9, 2325-2328; (g) Barrero AF, Alvarez-Manzaneda EJ, Chahboun R, Cortes M, Armstrong V. (1999) Synthesis and antitumor activity of puupehedione and related compounds. Tetrahedron, 55, 15181-15208; (h) Barrero AF, Altarejos J, Alvarez-Manzaneda EJ, Ramos JM, Salido S. (1996) Synthesis of (±)-ambrox from (E)-nerolidol and β-ionone via allylic alcohol [2,3] sigmatropic rearrangement. Journal of Organic Chemistry, 61, 2215-2218.
11.
BarreroA.F., HerradorM.M., ArteagaP., DiéguezH.R. (2010) Procedimiento para la obtención de productos olorosos a partir de la planta Bellardia trixago. Patent No. ES 2324761 and WO 2010103145.
KongkathipB., KongkathipN., JanthornS., VirarangsiyakornD. (1999) Stereospecific total synthesis of amberketal and a homolog. Chemistry Letters, 51–52.
14.
JegouE., PolonskyJ., LedererE., Schulte-ElteK-H, EggerB., OhloffG. (1977) Ambergris revisited. Isolation of volatile constituents; identification and synthesis of ambra-aldehyde C14H22O. Nouveau Journal de Chimie, 1, 529–531.
