Enantioselective catalytic approach to the C23-C28 subunit of 24α-methyl steroids

Viktoryia S Yakimchyk; Volha V Kazlova; Alaksiej L Hurski; Rimma G Savchenko; Svetlana A Kostyleva; Vladimir N Zhabinskii; Vladimir A Khripach

doi:10.1016/j.steroids.2019.05.003

Enantioselective catalytic approach to the C23-C28 subunit of 24α-methyl steroids

Steroids. 2019 Aug:148:82-90. doi: 10.1016/j.steroids.2019.05.003. Epub 2019 May 15.

Authors

Viktoryia S Yakimchyk¹, Volha V Kazlova¹, Alaksiej L Hurski², Rimma G Savchenko³, Svetlana A Kostyleva⁴, Vladimir N Zhabinskii⁵, Vladimir A Khripach⁶

Affiliations

¹ Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, Kuprevich Str., 5/2, 220141 Minsk, Belarus.
² Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, Kuprevich Str., 5/2, 220141 Minsk, Belarus. Electronic address: ahurski@iboch.by.
³ Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prosp. Oktyabrya 141, 450075 Ufa, Russian Federation. Electronic address: rimasavchenko@mail.ru.
⁴ Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prosp. Oktyabrya 141, 450075 Ufa, Russian Federation. Electronic address: khripach@iboch.by.
⁵ Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, Kuprevich Str., 5/2, 220141 Minsk, Belarus. Electronic address: vz@iboch.by.
⁶ Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, Kuprevich Str., 5/2, 220141 Minsk, Belarus. Electronic address: khripach@iboch.by.

PMID: 31100291
DOI: 10.1016/j.steroids.2019.05.003

Abstract

Enantioselective synthesis of C23-C28 subunit of campestane steroids based on catalytic methods is reported. The synthesis was started from (S)-2-isopropyl-4-nitrobutan-1-ol, which is easily accessible by the reaction between isovaleraldehyde and nitroethylene catalyzed by only 2% of (S)-trimethylsilyldiphenylprolinol. Removal of one "extra" carbon from the nitroalcohol was achieved by Ni-catalyzed hydrodecarboxylation of the redox-active ester intermediate. The synthesized C23-C28 fragment was attached to a steroidal core by Julia-Kocienski reaction of a steroidal aldehyde with metallated C23-C28 sulfone. The obtained product of olefination was easily transformed to a precursor of campesterol and (Z)-22-dehydrocampesterol.

Keywords: Campesterol; Decarbonylation; Michael addition; Ni-catalyzed decarboxylation; cis-22-Dehydrocampesterol.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Catalysis
Molecular Conformation
Pyrrolidines / chemistry*
Stereoisomerism
Steroids / chemical synthesis*
Steroids / chemistry

Substances

Pyrrolidines
Steroids
diphenylprolinol