Biomimetic synthesis of meroterpenoids by dearomatization-driven polycyclization
Files
Accepted manuscript
Date
2019-11-04
Authors
Powers, Zachary
Scharf, Adam
Cheng, Andrea
Yang, Feng
Himmelbauer, Martin
Mitsuhashi, Takaaki
Barra, Lena
Taniguchi, Yoshimasa
Kikuchi, Takashi
Fujita, Makoto
Version
Accepted manuscript
OA Version
Citation
Zachary Powers, Adam Scharf, Andrea Cheng, Feng Yang, Martin Himmelbauer, Takaaki Mitsuhashi, Lena Barra, Yoshimasa Taniguchi, Takashi Kikuchi, Makoto Fujita, Ikuro Abe, John A Porco. 2019. "Biomimetic Synthesis of Meroterpenoids by Dearomatization-Driven Polycyclization.." Angew Chem Int Ed Engl, Volume 58, Issue 45, pp. 16141 - 16146. https://doi.org/10.1002/anie.201910710
Abstract
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.
Description
Published in final edited form as: Angew Chem Int Ed Engl. 2019 November 04; 58(45): 16141–16146. doi:10.1002/anie.201910710.