Steroidal cyclobutanones. Part 2. Diastereofacial selection in the cycloaddition of dichloroketene and 3β-acetoxy-20a-homopregna-5,20-diene. Crystal structure of the cycloadduct, (20S)-3β-acetoxy-20,24-cyclo-22,22-dichlorochol-5-en-23-one

Abstract

The reaction of dichloroketene and 3β-acetoxy-20a-homopregna-5,20-diene 1 is shown to give one diastereoisomeric cycloadduct 2 arising from attack at the rear side of the preferred rotamer 1b of the steroid skeleton. The structure of dichlorocyclobutanone 2 was determined by X-ray crystallography. Reduction of 2 gives chlorocyclobutanone 3 and cyclobutanone 4. Examination of the cyclobutanones by CD, ¹H and ¹³C NMR spectroscopy demonstrates that these techniques can be used for the determination of the configuration of 2 and 3.