148.Total Synthesis of (+)-Haperforin G

Wei Zhang, Zhenyu Zhang, Jun-Chen Tang, Jin-Teng Che, Hao-Yu Zhang, Jia-Hua Chen,* and Zhen Yang*

J. Am. Chem. Soc. 2020, 142(46), 19487–19492

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