TERPENOIDS. XL.¹ ABSOLUTE CONFIGURATION OF EREMOPHILONE²

Abstract

Therefore the indications are that the transitory phosphorylation product is either unstable or remains enzyme-bound. The results presented support the concerted mechanism shown below.

Absolute configuration of eremophilane sesquiterpenes from Petasites hybridus: Comparison of experimental and calculated circular dichroism spectra

“…They succeeded in synthetisizing a common degradation product, trans-5,10-dimethyl-3a-isopropyl-decalone-2, from an intermediate of known absolute configuration. 12,13 Their proposal for the absolute configuration of hydroxyeremophilone and its derivatives was verified in 1966 by comprehensive ORD and NMR experiments.…”

“…They further investigated dispersion curves of several transformation products of eremophilone to confirm their new stereochemical assignment. 11 The absolute configurations of eremophilone and the closely related hydroxydihydroeremophilone and hydroxyeremophilone were established by Djerassi and coworkers 12,13 a few years later. They succeeded in synthetisizing a common degradation product, trans-5,10-dimethyl-3a-isopropyl-decalone-2, from an intermediate of known absolute configuration.…”

Total synthesis of eremophilone

“…The combined ethereal extracts were washed with dilute HC1 and with saturated brine, then filtered, dried (NaaSOJ, and concentrated to give a pale yellow oil [10.4 g, 95%, bp 50°(2 mm)] whose physical properties correspond to those reported. 10 4-(l'-Ácetoxyisopropyl)-2-methylcyclohexanone (6). 3-Methylnopinone was treated with aqueous sulfuric acid exactly as reported15 to give 4-(l,-hydroxyisopropyl)-2-methylcyclohexanone (5) in 75% yield.…”