title: Total syntheses of the squalene-derived halogenated polyethersent-dioxepandehydrothyrsiferol and armatol A via bromonium- and Lewis acid-initiated epoxide-opening cascades.
abstract: Herein we describe in full our investigations leading to the first total syntheses ofent-dioxepandehydrothyrsiferol and armatol A. Discovery of a bromonium-initiated epoxide-opening cascade enabled novel tactics for constructing key fragments found in both natural products and have led us to revise the proposed biogeneses. Other common features found in the routes include convergent fragment coupling strategies to assemble the natural products' backbones and the use of epoxide-opening cascades for rapid constructions of the fused polyether subunits. Throughde novosynthesis of armatol A, we elucidate the absolute and relative configuration of this natural product.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA 02139, USA.
authors.forename: Brian S
authors.initials: BS
authors.lastname: Underwood
authors.forename: Jessica
authors.initials: J
authors.lastname: Tanuwidjaja
authors.forename: Sze-Sze
authors.initials: SS
authors.lastname: Ng
authors.forename: Timothy F
authors.initials: TF
authors.lastname: Jamison
keywords: Epoxidation; Natural products; Structure elucidation; Terpenoids; Total synthesis