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Total Synthesis of the Diterpenoid Alkaloid Arcutinidine Using a Strategy Inspired by Chemical Network Analysis

preprint
submitted on 30.05.2019, 04:04 and posted on 30.05.2019, 15:36 by Kyle Owens, Shelby McCowen, Katherine Blackford, Sohei Ueno, Yasuo Hirooka, Manuel Weber, Richmond Sarpong
Arcutinidine and other arcutinidine-type diterpenoid alkaloids feature an intricate polycyclic, bridged framework with unusual connectivity. A chemical network analysis approach to the arcutane skeleton enabled the identification of highly simplifying retrosynthetic disconnections, which indicated that the caged structure could arise from a simpler fused ring system. On this basis, a total synthesis of arcutinidine is reported herein, featuring an unprecedented oxopyrrolium Diels–Alder cycloaddition which furnishes a key tetracyclic intermediate. In addition, the synthesis utilizes a diastereoselective oxidative dearomatization/cycloaddition sequence and a SmI2-mediated C–C coupling to forge the bridged framework of the natural products. This synthetic plan may also enable future investigations into the biosynthetic relationships between the arcutanes, the related diterpenoid atropurpuran, and other diterpenoid alkaloids.

History

Email Address of Submitting Author

kylerowens@gmail.com

Institution

UC Berkeley

Country

United States

ORCID For Submitting Author

0000-0003-3076-053X

Declaration of Conflict of Interest

No conflicts of interest

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ChemRxiv

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