Perillyl alcohol-8,9-epoxide

Further variations on the epoxyketone intermediate theme have been reported. In the first (Scheme 9A) [78], limonene oxide was prepared by Sharpless asymmetric epoxidation of commercial (S)-(-)- perillyl alcohol 65 followed by conversion of the alcohol 66 to the crystalline mesylate, recrystallization to remove stereoisomeric impurities, and reduction with LiAlH4 to give (-)-limonene oxide 59. This was converted to the key epoxyketone 60 by phase transfer catalyzed permanganate oxidation. Control of the trisubstituted alkene stereochemistry was achieved by reaction of the ketone with the anion from (4-methyl-3-pentenyl)diphenylphosphine oxide, yielding the isolable erythro adduct 67, and the trisubstituted E-alkene 52a from spontaneous elimination by the threo adduct. Treatment of the erythro adduct with NaH in DMF resulted... 

Cyclohexene epoxide. See Cyclohexene oxide Cyclohexene, 4-ethenyl-. See 4-Vi nylcyclohexene Cyclohex-1-ene-1-methanol, 4-(1-methylethenyl)-. See Perillyl alcohol 3-Cyclohexene-1-methanol, a,o, 4-trimethyl-. 

Perillyl alcohol (74 ) was epoxidized by Streptomyces ikutamanensis Ya-2-1 to give 8,9-epoxy-(-)-perillyl alcohol (77 ) (Noma et al., 1986) (Figure 14.100). 

FIGURE 19.100 Biotransformation of (-)-perillyl aicohoi (74 ) by Streptomyces ikutamanensis Ya 2 1. (Modi ed from Noma, Y. et al., Reduction of terpene aldehydes and epoxidation of terpene alcohols by S. ikutamanensis, Ya-2-1, Proceedings of 30th TEAC, 1986, pp. 204-206.)... 

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