A common variety of Myopovum deserti A. Cunn. (Ellangowan Poison Bush) yields an essential oil consisting largely of the iridoid monoterpene, (1R)-1-methoxymyodesert-3-ene, C11Hls02, (1 R,4aS,7R,7aR)-1-methoxy-4,7-dimethyl-l,4a,5,6,7,7a-hexahydrocycopenta[c]pyran, b.p. 6772 mm, [@lo -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, (lR,4R,4aR,7R,7aR)-4,7-dimethyl-1,3,4,4a,5,6,7,7a-octahydrocyclopenta[c]pyran-1-01, Oxidation of this 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. Treatment 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 a-and j3-anomers. Spectral studies of these and other products establish the configuration of the natural product at C 1.(1R)-1-Methoxymyodesert-3-ene is not toxic to sheep as are the j3-substituted furans characteristic of most other chemovarieties of M. desevti.The shrub Myoporum deserti A. Cunn. (Ellangowan Poison Bush), which is found in the drier areas of Australia, is a well authenticated stock poison.' Previous parts2 of this series have described the isolation and chemistry of 11 toxic furanoid sesquiterpene ketones, such as (1) and (2), from various chemovarieties of the species but certain others contain iridoid monoterpenes accompanied by little or none of the toxic furanoid derivatives.