Biosynthesis of Polycyclic Natural Products from Conjugated Polyenes via Tandem Isomerization and Pericyclic Reactions
Kanji Niwa, Masao Ōhashi, Kaili Xie, Chen‐Yu Chiang, Cooper S. Jamieson, Michio Sato, Kenji Watanabe, Fang Liu, K. N. Houk, Yi Tang
Abstract
We report biosynthetic pathways that can synthesize and transform conjugated octaenes and nonaenes to complex natural products. The biosynthesis of (-)-PF1018 involves an enzyme PfB that can control the regio-, stereo-, and periselectivity of multiple reactions starting from a conjugated octaene. Using PfB as a lead, we discovered a homologous enzyme, BruB, that facilitates diene isomerization, tandem 8π-6π-electrocyclization, and a 1,2-divinylcyclobutane Cope rearrangement to generate a new-to-nature compound.
Topics & Concepts
ChemistryPericyclic reactionIsomerizationConjugated systemTandemBiosynthesisCope rearrangementCascade reactionEnzymeStereochemistryCombinatorial chemistryOrganic chemistryCatalysisComposite materialPolymerMaterials scienceMicrobial Natural Products and BiosynthesisPlant biochemistry and biosynthesisMicrobial Metabolic Engineering and Bioproduction