Total Synthesis of (+)–Haperforin G

(+)-Haperforin G was synthesized in 20 steps from commercially available starting materials. A Co-catalyzed intramolecular Pauson–Khand reaction was used for stereoselective construction of cyclopentanone bearing an all-carbon quaternary stereogenic center at the bridge-head position. Light-initiated photocatalysis was used for convergent and asymmetric cross-coupling of the unstabilized C(sp³) radical with an enone. The developed chemistry paves the way to the synthesis of structurally diverse analogs of haperforin G (6).