Powers, ZacharyScharf, AdamCheng, AndreaYang, FengHimmelbauer, MartinMitsuhashi, TakaakiBarra, LenaTaniguchi, YoshimasaKikuchi, TakashiFujita, MakotoAbe, IkuroPorco, John A.2020-12-152020-12-152019-11-04Zachary 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.2019107101521-3773https://hdl.handle.net/2144/41804Published in final edited form as: Angew Chem Int Ed Engl. 2019 November 04; 58(45): 16141–16146. doi:10.1002/anie.201910710.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.p. 16141 - 16146en-US3,5-dimethylorsellinic acidBiosynthesisDearomatizationMeroterpenoidsPolyene cyclizationBiomimeticsCyclizationPolyenesPolyisoprenyl phosphatesSesquiterpenesTerpenesOrganic chemistryChemical sciencesArticle10.1002/anie.201910710488547