Abstract
AbstractReduction of the acetoxymethylene ketone 1b yielded a mixture of two epimeric diols 3a and 4a, which were converted into the p‐toluenesulfonates 3d and 4d. Solvolysis of 3d in dry acetic acid afforded 5b after inversion at C‐17. As an explanation for the formation of 5b, it was assumed that the cyclic cation 8 may be an intermediate. This was confirmed by methanolysis of 3d leading to the orthoester 10. The neighbouring group participation (AcO‐6) observed during solvolysis of 3d was completely absent in the case of 4d, solvolysis of which yielded 17β‐acetoxy‐16α‐acetoxymethyl‐3‐methoxyestra‐1,3,5(10)‐triene (4b) with retention in both acetic acid and methanol.
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