Sinomenineの還元成績体に関する研究 (第4報)

SinomeninolおよびDihydrosinomeninolの配位の考察

抄録

Acetylation of methylsinomeninol and methyldihydrosinomeninol was carried out with their respective epimers and it was found that the hydroxyl at 6-position with A-type configuration was far more reactive. This fact suggests that the hydroxyl at 6-position of methylsinomeninol-A (III) and methyldihydrosinomeninol-A (VI) takes the equatorial configuration. Sinomeninol-B 4-acetate (XII) undergoes acyl migration during alumina chromatography and forms sinomeninol-B 6-acetate (XIII). These facts suggest that the hydroxyl at 6-position of sinomeninol-B (XI) and methylsinomeninol-B (IV) takes axial configuration. The optical rotation of sinomeninol and methylsinomeninol shows greater degree of dextrorotation in A-type configuration, which is not inconsistent with Mills' rule.