Biomimetic synthesis of meroterpenoids by dearomatization-driven polycyclization
Powers, Zachary; Scharf, Adam; Cheng, Andrea; Yang, Feng; Himmelbauer, Martin; Mitsuhashi, Takaaki; Barra, Lena; Taniguchi, Yoshimasa; Kikuchi, Takashi; Fujita, Makoto; Abe, Ikuro; Porco, John A.
A biomimetic route to farnesyl pyrophosphate and dimethyl orsellinic acid (DMOA)-derived meroterpenoid scaffolds has yet to be reported despite great interest from the chemistry and biomedical research communities. A concise synthetic route with the potential to access DMOA-derived meroterpenoids is highly desirable to create a library of related compounds. Herein, we report novel dearomatization methodology followed by polyene cyclization to access DMOA-derived meroterpenoid frameworks in six steps from commercially available starting materials. Furthermore, several farnesyl alkene substrates were used to generate structurally novel, DMOA-derived meroterpenoid derivatives. DFT calculations combined with experimentation provided a rationale for the observed thermodynamic distribution of polycyclization products.
Published in final edited form as: Angew Chem Int Ed Engl. 2019 November 04; 58(45): 16141–16146. doi:10.1002/anie.201910710.
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