A unified approach to meroterpenoids applanatumols B, V, W, X, and Y produced by the medicinal fungus Ganoderma applanatum and 2'-epi-spiroapplanatumine O is presented. The key synthetic sequence consists of a tandem anionic ketone allylation/oxy-Cope rearrangement/α-oxygenation furnishing an α-aminoxy ketone and a persistent radical effect-based 5-exo-trig cyclization leading to the trisubstituted cyclopentane core. The relative configuration of applanatumol V has to be revised. Some compounds display significant cytotoxic and antioxidant properties.

Department of Inorganic Chemistry Faculty of Science Charles University Prague Hlavova 2030 8 12843 Prague 2 Czech Republic

Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo náměstí 2 16610 Prague 6 Czech Republic

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Total Synthesis of Ganoapplanin Enabled by a Radical Addition/Aldol Reaction Cascade