Synthesis of 3β-Hydroxytaxodione and Coleons S and T

Article abstract of DOI:10.1246/bcsj.55.1168

Hinokiol diacetate was converted into 3β-acetoxyabieta-8,11,13-triene-6β,12-diol via 3β,12-diacetoxyabieta-8,11,13-trien-7-one and 3β,12-diacetoxyabieta-6,8,11,13-tetraene.Oxidation of the 6β,12-diol with benzoyl peroxide produced 3β-acetoxy-12-benzoyloxyabieta-8,11,13-triene-6β,11-diol, which was converted into 3β,11,12-triacetoxyabieta-8,11,13-trien-6-one by lithium aluminium hydride reduction, acetylation, and Jones oxidation.Acidic hydrolysis of the triacetoxy ketone, followed by column chromatography on silica gel, afforded 3β-hydroxytaxodione.Oxidation of the 6β,11-diol with m-chloroperbenzoic acid afforded 3β-acetoxy-12-benzoyloxy-6β-hydroxyabieta-8,12-diene-11,14-dione.This was further converted into 3β,11,14-triacetoxy-12-benzoyloxyabieta-8,11,13-triene-6,7-dione by a series of reactions: Jones oxidation, reduction with zinc powder and dilute hydrochloric acid, acetylation, and Jones oxidation.Alkaline hydrolysis of the 6,7-dioxo compound afforded coleon T, which was isomerized to coleon S by refluxing with concentrated hydrochloric acid in methanol.