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(5)-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.