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13-Step Total Synthesis of Atropurpuran

Author:
Xie, Shengling, Chen, Gui, Yan, Hao, Hou, Jieping, He, Yongping, Zhao, Tongyun, Xu, Jing
Source:
Journal of the American Chemical Society 2019 v.141 no.8 pp. 3435-3439
ISSN:
1520-5126
Subject:
diterpenoid alkaloids, moieties, regioselectivity
Abstract:
Herein, we report a concise total synthesis of atropurpuran, a unique and synthetically challenging pentacyclic diterpene that bears a tetracyclo[5.3.3.0⁴,⁹.0⁴,¹²]-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[5.3.3.0⁴,⁹.0⁴,¹²]-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.
Agid:
6324000