13-Step Total Synthesis of Atropurpuran XieShengling ChenGui YanHao HouJieping HeYongping ZhaoTongyun XuJing 2019 Herein, we report a concise total synthesis of atropurpuran, a unique and synthetically challenging pentacyclic diterpene that bears a tetracyclo­[5.3.3.0<sup>4,9</sup>.0<sup>4,12</sup>]-tridecane skeleton that is unprecedented among natural terpenes. This 13-step approach features a strategy that include early stage rapid skeleton formation and the late-stage introduction of reactive functional groups, thus allowed a high overall synthetic efficiency with minimal use of PGs. The key transformations of our work include a facile construction of the spiro[5.5]­undecane moiety through an ring-closing enyne metathesis reaction and an efficient formation of the tetracyclo­[5.3.3.0<sup>4,9</sup>.0<sup>4,12</sup>]-tridecane scaffold via an regioselective double oxidative dearomatization/intramolecular Diels–Alder reaction cascade. This efficient approach should also inspire further advances in the synthesis of related complex diterpenes and diterpenoid alkaloids.