173.Total Synthesis of (+)−Haperforin G

Zhenyu Zhang, Wei Zhang, Jun−Chen Tang, Jin−Teng Che, Zhongchao Zhang, Jia−Hua Chen,*and Zhen Yang*

J. Org. Chem. 2023, 88(15), 10539−10554

(+)-Haperforin G was synthesizedin 20 steps from commerciallyavailable starting materials. A Co-catalyzed intramolecular Pauson-Khandreaction was used for stereoselective construction of cyclopentanonebearing an all-carbon quaternary stereogenic center at the bridge-headposition. Light-initiated photocatalysis was used for convergent andasymmetric cross-coupling of the unstabilized C(sp(3)) radicalwith an enone. The developed chemistry paves the way to the synthesisof structurally diverse analogs of haperforin G (6).