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DOI: 10.1039/A807082B (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 1, 1998, 4121-4128

Azasteroids derived from fusidic acid

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William S. Murphy, Basil Sarsam, George Ferguson and John F. Gallagher

Abstract

The Beckmann rearrangement pathway of the (E[hair space])-11-oxime 6, derived from fusidic acid, one of the uncommon 9β-steroids with ring B constrained in a boat conformation, was investigated. It was found that 6 was converted into methyl 3-O-acetyl-11-aza-11a-homo-11a-oxo-24,25-dihydrofusidate 7, the ‘normal’ product of rearrangement, when treated with toluene-p-sulfonyl chloride in pyridine. The structure and stereochemistry of 7 was determined by X-ray crystallography. The absolute configuration of fusidic acid was confirmed. The Beckmann rearrangement of the oxime derivatives of 3- and 17-oxo-9β-steroids derived from fusidic acid was also investigated. In general, with the exception of the (E[hair space])-oxime of 17-oxotriacetate 13b, which resulted in a complex mixture of products, none of which predominated, all the oximes gave the normal Beckmann rearrangement products.

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