A very short synthesis of steroids from 1,3-butadiene and benzocyclobutenes.
Lewis acid mediated addition of 1,8-bis(trimethylsilyl)octa-2,6-diene (BISTRO) 1 to succinic anhydride led to spirolactone 2 [(+/-)-6,9-divinyl-1-oxaspiro[4.4]nonan-2-one]. Methoxycarbonylation followed by stereoselective alkylation by various benzocyclobutenes afforded the substituted benzocyclobutene steroid precursors 5. Thermolysis of 5 gave rise to steroids (+/-)-6 with a trans-anti-cis configuration in five steps and in a highly stereoselective manner. Modifications of the sequence allowed the preparation of steroids (+/-)-11 with trans-anti-trans configuration.
Michellys
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Laboratoire de Synthèse Organique, UMR-CNRS no. 6009, Faculté des Sciences de St Jérôme, 13397 Marseille, France.
Maurin
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Toupet
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Pellissier
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Santelli
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D000478:Alkylation; D002070:Butadienes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D011083:Polycyclic Compounds / Q000737:chemistry*; D013148:Spironolactone / Q000138:chemical synthesis; D013237:Stereoisomerism; D013256:Steroids / Q000138:chemical synthesis* / Q000737:chemistry
D002070:Butadienes; D007202:Indicators and Reagents; D011083:Polycyclic Compounds; D013256:Steroids; D013148:Spironolactone; C079040:benzocyclobutene; C031763:1,3-butadiene