Zhihui Huang, Dr. Jun Huang, Yongzheng Qu, Weibin Zhang, Prof. Dr. Jianxian Gong*, Prof. Dr. Zhen Yang*

Angew. Chem. Int. Ed. 2018, 57(28), 8744 –8748

• Highlighted in Synfacts, 2018, 14, 788.

Efficient total syntheses of the naturally occurring, potent antibiotic compounds (−)‐crinipellin A and (−)‐crinipellin B are described. The key advanced intermediate, a fully functionalized tetraquinane core, was constructed by a novel thiourea/palladium‐catalyzed Pauson–Khand reaction. This intermediate can serve as a common intermediate for the collective total synthesis of other members of the crinipellin family.