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An efficient and enantioselective route toward an architecturally unusual ergostane-type steroid, dankasterone B, is presented. The cis-decalin skeleton of the steroid was established by an intramolecular metal-catalyzed hydrogen atom transfer (MHAT) reaction. A radical rearrangement was used to construct the 13(14 → 8)abeo-ergostane skeleton.

Graphical abstract: Formal total synthesis of dankasterone B

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