Conversion of Phorbol into Des-D-Ring Tricycle and Crotonianoid B via Peroxidation Reaction.

Org Lett

Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

Published: May 2024

Phorbol () has a tetracyclic ABCD-ring and is readily isolable from a natural source. We previously synthesized and 16 structurally related natural products using common ABC-ring intermediate . Here we report a new synthetic route to using as a starting material. Key features of the synthesis are chemoselective removal of the D-ring via cyclopropane opening, peroxidation, and retro-aldol reactions. The high utility of the peroxidation was further demonstrated in the first synthesis of crotonianoid B ().

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http://dx.doi.org/10.1021/acs.orglett.4c01363DOI Listing

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