Terpenoid chemistry. xxiv* (1r)-1-methoxymyodesert-3-ene, an iridoid constituent of myoporum deserti (myoporaceae)

H.G.Grant H.G.GrantHamish G.H.G.Grant H.GrantHamish G.https://api.elsevier.com/content/author/author_id/7005379128 (1980) Terpenoid chemistry. xxiv* (1r)-1-methoxymyodesert-3-ene, an iridoid constituent of myoporum deserti (myoporaceae). Australian Journal of Chemistry, 33 4: 853-878. doi:10.1071/CH9800853


Author H.G.Grant H.G.GrantHamish G.H.G.Grant H.GrantHamish G.https://api.elsevier.com/content/author/author_id/7005379128
Title Terpenoid chemistry. xxiv* (1r)-1-methoxymyodesert-3-ene, an iridoid constituent of myoporum deserti (myoporaceae)
Journal name Australian Journal of Chemistry
ISSN 14450038 00049425
Publication date 1980-01-01
Sub-type Article (original research)
DOI 10.1071/CH9800853
Open Access Status Not yet assessed
Volume 33
Issue 4
Start page 853
End page 878
Total pages 26
Language eng
Subject 1600 Chemistry
Abstract A common variety of Myoporum deserti A. Cunn. (Ellangowan Poison Bush) yields an essential oil consisting largely of the iridoid monoterpene, (1R)-1-methoxymyodesert-3-ene, CHO, (1A, 4aS, 7R, 7aR)-1-methoxy-4, 7-dimethyl-1, 4a, 5, 6, 7, 7a-hexahydrocyclopenta[c]pyran, b.p. 67°/2mm, [α] - 165°. This cyclic acetal is hydrolysed to methanol and a mixture of two epimeric cyclopentanoid dialdehydes which are oxidized to the two epimeric trans, trans-nepetalinic acids and yield (+)-(R)-actinidine with Brady’s reagent. (1R)-1-Methoxymyodesert-3-ene is oxidized by ozone/hydrogen peroxide to (1R, 2R, 5R)-2-acetyl-5-methylcyclopentanecarboxylic acid. Hydrogenation yields mainly (1R)-methoxymyodesertan, hydrolysed by aqueous maleic acid at room temperature to methanol and a cyclic hemiacetal, (1R, 4R, 4aR, 7R, 7aR)-4, 7-dimethyl-1, 3, 4, 4a, 5, 6, 7, 7a-octahydrocyclopenta[c]pyran-1-ol. Oxidation of this cis, cis-hemiacetal by bromine in acetate buffer yields a lactone further oxidized by chromic acid to (2R, 1′S, 2′R, 3′R)-2-(2′-carboxy-3′-methylcyclopentyl)-propionic acid. (1R)-1-Methoxymyodesertan, refluxed with aqueous phthalic acid, yields (+)-(4R, 4aR, 7R)- 4, 7-dimethyl-3, 4, 4a, 5, 6, 7-hexahydrocyclopenta[c]pyran.T reatment of the hexahydropenta[c]pyran, the cis, cis-hemiacetal or (1R)-1-methoxymyodesertan with hydrochloric acid yields a tvans, transhemiacetal, (1 R, 4R, 4aR, 7R, 7aS)-4, 7-dimethyl-1, 3, 4, 4a, 5, 6, 7, 7a-octahydrocyclopenta[c]pyran-l-ol, which equilibrates in solution to a mixture of α and βanomers. Spectral studies of these and other products establish the configuration of the natural product at C 1. (1R)-1-Methoxymyodesert-3-eneis not toxic to sheep as are the β-substituted furans characteristic of most other chemovarieties of M. desevti.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Scopus Import - Archived
 
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Created: Tue, 12 Sep 2017, 00:04:40 EST by System User