Total Syntheses of Polycyclic Diterpenes Phomopsene, Methyl Phomopsenonate, and iso-Phomopsene via Reorganization of C–C Single Bonds

The first total syntheses of polycyclic diterpenes phomopsene (1), methyl phomopsenonate (2), and iso-phomopsene (3) have been accomplished through the unusual cascade reorganization of C–C single bonds. This approach features: (i) a synergistic Nazarov cyclization/double ring expansions in one-step...

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Published in:Journal of the American Chemical Society 2023-10, Vol.145 (39), p.21170-21175
Main Authors: Yin, Jun-Jie, Wang, Yun-Peng, Xue, Jun, Zhou, Feng-Fan, Shan, Xing-Qian, Zhu, Rong, Fang, Kun, Shi, Lei, Zhang, Shu-Yu, Hou, Si-Hua, Xia, Wujiong, Tu, Yong-Qiang
Format: Article
Language:English
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Summary:The first total syntheses of polycyclic diterpenes phomopsene (1), methyl phomopsenonate (2), and iso-phomopsene (3) have been accomplished through the unusual cascade reorganization of C–C single bonds. This approach features: (i) a synergistic Nazarov cyclization/double ring expansions in one-step, developed by authors, to rapid and stereospecific construction of the 5/5/5/5 tetraquinane scaffold bearing contiguous quaternary centers and (ii) a one-pot strategic ring expansion through Beckmann fragmentation/recombination to efficiently assemble the requisite 5/5/6/5 tetracyclic skeleton of the target molecules 1–3. This work enables us to determine that the correct structure of iso-phomopsene is, in fact, the C7 epimer of the originally assigned structure. Finally, the absolute configurations of three target molecules were confirmed through enantioselective synthesis.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.3c07044