Synthesis of dehydro-oogoniol and oogoniol: The adrenosterone route

Article abstract of DOI:10.1016/S0040-4020(01)82010-X

Dehydro-oogoniol(3β, 11α, 15β,29-tetrahydroxystigmasta-5,24(28)(E)-dien-7-one), a female-activating hormone of the water mold Achlya, has been synthesized from 4-androstene-3,11,17-trione by a series of highly stereoselective reactions. One of these involved 1,4-addition of the magnesium cyanocuprate derivative of 3-(1,3-dioxolan-2-yl)-4-methylpentyl bromide to 3β-hydroxy-15β,16β-epoxy-11-oxo-(17E)-pregna -5, 17(20)-diene 3-tert -butyidimethylsilyl ether. The structure of an intermediate, 3β,11 β,15β-triacetoxy-5-cholesten-24-one, was confirmed by X-ray crystallographic analysis. Oogoniol [(24R)-3β,11α,15β,29-tetrahydroxy-stigmast-5-en-7-one] was synthesized in a similar manner by reaction of the magnesium cyanocuprate of (S)-3-(1-methylethyl)-5-[(tert-butyldimethylsilyl)oxy]pentyl bromide with the above epoxy pregnadiene.