Toward the Asymmetric de Novo Synthesis of Lanostanes: Construction of 7,11-Dideoxy-Δ 5 -lucidadone H

Efforts to establish an asymmetric entry to hexanorlanostanes has resulted in a concise synthesis of 7,11-dideoxy-Δ -lucidadone H from epichlorohydrin. By exploiting metallacycle-mediated annulative cross-coupling (to establish a functionalized hydrindane) and stereoselective formation of the steroi...

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Bibliographic Details
Published inJournal of organic chemistry Vol. 87; no. 21; pp. 14975 - 14979
Main Authors Wai, HtooTint, Micalizio, Glenn C
Format Journal Article
LanguageEnglish
Published United States 04.11.2022
Subjects
Epichlorohydrin
Oxidation-Reduction
Stereoisomerism
Steroids
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Summary:Efforts to establish an asymmetric entry to hexanorlanostanes has resulted in a concise synthesis of 7,11-dideoxy-Δ -lucidadone H from epichlorohydrin. By exploiting metallacycle-mediated annulative cross-coupling (to establish a functionalized hydrindane) and stereoselective formation of the steroidal C9-C10 bond to establish a stereodefined 9-alkyl estrane, 14 subsequent steps have been established to generate a hexanorlanostane system. Key transformations include formal inversion of the C13 quaternary center, oxidative dearomatization/group-selective Wagner-Meerwein rearrangement, and Lewis acid mediated semi-Pinacol rearrangement.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.2c02042