Preparation of 3β‐Acetoxy‐17a‐Oxo‐Androst‐5‐Ene‐7,17‐Dione, a Biologically Active Impurity Isolated from the Production of 3β‐Acetoxyandrost‐5‐Ene‐7,17‐Dione

Abstract

An impurity isolated during the kilo‐lab preparation of 3β‐acetoxyandrost‐5‐ene‐7,17‐dione was identified as 3β‐acetoxy‐17a‐oxo‐androst‐5‐ene‐7,17‐dione. This novel D‐ring secosteroid was postulated to be a Baeyer–Villiger oxidation by‐product of the preparation reaction. A genuine sample was prepared by the selective peracid‐mediated Baeyer–Villiger reaction on 3β‐acetoxyandrost‐5‐ene‐7,17‐dione (7‐oxo‐DHEA acetate), confirming the novel structure.

Keywords:

• 3β‐Acetoxyandrost‐5‐ene‐7,17‐dione
• allylic oxidation
• Baeyer–Villiger oxidation
• lactone
• 7‐oxo‐DHEA acetate

Acknowledgment

Albany Molecular Research, Inc. thanks Henry Lardy for an authentic sample of 4 and for his exciting and enlightening discussion during this project. We also thank Humanetics Corporation, Chanhassen, Minnesota, for their permission to publish this article. The authors thank Sandy Birk for her assistance in the preparation of this paper.

Notes

^†Trade name: 7‐Keto™, developed and distributed by Humanetics Corporation, Chanhassen, MN 55317.