title: A biomimetic synthesis of (±)-basiliolide B.
abstract: A highly diastereoselective and practical biomimetic total synthesis of (±)-basiliolide B has been achieved through the study of the two proposed biosynthetic pathways (O-methylation and O-acylation) for the unprecedented 7-methoxy-4,5-dihydro-3H-oxepin-2-one (C ring). The synthesis featured a cyclopropanation/ring opening strategy for establishing the stereogenic centers at C8 and C9, a biomimetic 2-pyrone Diels-Alder cycloaddition for the synthesis of the ABD ring system, and finally a highly efficient biomimetic intramolecular O-acylation for the C ring formation. This result provides an important perspective on the biosynthetic origin of the unprecedented 7-membered acyl ketene acetal moiety of the C ring.
authors.affiliation: Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen University Town, Xili, Shenzhen 518055 (China).
authors.forename: Long
authors.initials: L
authors.lastname: Min
authors.forename: Yang
authors.initials: Y
authors.lastname: Zhang
authors.forename: Xuefeng
authors.initials: X
authors.lastname: Liang
authors.forename: Junrong
authors.initials: J
authors.lastname: Huang
authors.forename: Wenli
authors.initials: W
authors.lastname: Bao
authors.forename: Chi-Sing
authors.initials: CS
authors.lastname: Lee
mesh_terms: D000215:Acylation; D032701:Biomimetics; D061565:Cycloaddition Reaction; D011753:Pyrones / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: C584017:2-pyrone; D011753:Pyrones; C543083:basiliolide B
keywords: Diels-Alder reaction; O-acylation; basiliolide B; biomimetic synthesis; cyclopropanation