SYNTHESIS OF 17R)-17-HYDROXY-14,15-SECOANDROST-4-EN-15-YN-3-ONE AND 17S)-17-HYDROXY-14,15-SECOANDROST-4-EN-15-YN-3-ONE AND THE X-RAY CRYSTAL-STRUCTURE OF THE (17S)-DIASTEREOMER
Yf. Hu et al., SYNTHESIS OF 17R)-17-HYDROXY-14,15-SECOANDROST-4-EN-15-YN-3-ONE AND 17S)-17-HYDROXY-14,15-SECOANDROST-4-EN-15-YN-3-ONE AND THE X-RAY CRYSTAL-STRUCTURE OF THE (17S)-DIASTEREOMER, Steroids, 60(6), 1995, pp. 491-496
R,S)-17-Hydroxy-14,15-secoandrost-4-en-15-yn-3-one has been shown prev
iously to be a mechanism-based inactivator of rat liver 3 alpha-hydrox
ysteroid dehydrogenase. This manuscript describes the synthesis of thi
s diastereomeric 14,15-secosteroid from [2S-(2 alpha,4a alpha,4b beta,
10a 3,4a,4b,7,9,10,10a-decahydro-2,4b-dimethyl-7-oxa-2 -phenanthreneca
rboxylic acid methyl ester. The separation of this diastereomeric 14,1
5-secosteroid into (17R)- and 17S)-17-hydroxy-14,15-secoandrost-4-en-1
5-yn-3-one was accomplished by HPLC separation of the 4-methylphenyl)s
ulphonyl]-2-pyrrolidinecarbonylate derivatives an a silica column. The
crystal structure of 17S)-17-hydroxy-14,15-secoandrost-4-en-15-yn-3-o
ne was then solved by X-ray diffraction analysis to establish unambigu
ously the absolute configuration of the diastereomeric 14,15-secostero
id.