The synthesis of oxiranes from 3-and 17-keto steroids is described. Dimethylsulfonium methylide (1) reacted with estrone in a highly stereoselective manner by aside addition of CH2. or-Side addition also predominated in the reaction of 1 with 3-keto-5or steroids (although an earlier claim of stereospecificity has to be modified to stereoselectivity), whereas dimethyloxosulfonium methylide (2) gave products resulting from p-side attack on the 3-keto group. Stereochemistry of the products was demonstrated by chemical conversions. The oxiranes reacted with amines to yield amino alcohols. Spiro-17p-oxiranylestra-1,3,5( lO)-trien-3-01 (4a) reacted with sodium cyanide a t steam-bath temperature to yield 17a-cyanomethyl-3,17p-estradiol (Se), but under more strenuous conditions the product of this reaction was estrone.
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