Thiosteroids—XXXIII: 10β-methylsulfonyl and 10β-phenylsulfonyl des-a-estr-9(11)-ene derivatives and their alkylation reaction: Synthesis of A-furanosteroids

摘要: Abstract The titled compounds, 12a , 12 b 21 a and 21b were synthesized by the reaction of α-sulfonyl carbanion generated from dimethyl sulfone or phenyl methyl with bisketal 9 7a-methyl-1,5-dioxo-3α,7aβ-hexahydroindan-4α-yl propionate prepared fermentation 5 subsequent oxidation product. Desulfurization ketals 21a gave des-A-steroid 3a . Michael addition 12b to vinyl ketone led corresponding adducts configurationally retained sulfonyl groups which converted 10β-methylsulfonyl 10β-phenyl-sulfonyl steroids 27a 27b 27c respectively. On other hand, α-bromoacetate yielded 29 desulfurization 30 identical product alkylation enamine 28 A-Furanosteroids 1a 37a its 1-methyl derivative. β axial configuration in compounds was evidenced PMR CD spectral data.