title: Total Synthesis of Brevisamide Using an Oxiranyl Anion Strategy.
abstract: A total synthesis of brevisamide, a marine monocyclic ether amide isolated from the dinoflagellate Karenia brevis, has been achieved in 18 steps starting from 4-(benzyloxy)butanol. The synthesis involves oxiranyl anion coupling between an epoxy sulfone and a triflate, intramolecular etherification of a hydroxy-bromoketone, diastereoselective introduction of the axial methyl group by hydroxyl-directed hydrogenation of an exocyclic olefin, and installation of an acetamide side chain by nucleophilic substitution of an N-acetyl carbamate. The dienal side chain is assembled using a Horner-Wadsworth-Emmons reaction to complete the synthesis.
authors.affiliation: Faculty of Pharmacy, Meijo University , 150 Yagotoyama, Tempaku-ku, Nagoya 468-8503, Japan.
authors.forename: Takeo
authors.initials: T
authors.lastname: Sakai
authors.affiliation: Faculty of Pharmacy, Meijo University , 150 Yagotoyama, Tempaku-ku, Nagoya 468-8503, Japan.
authors.forename: Ayumi
authors.initials: A
authors.lastname: Fukuta
authors.affiliation: Faculty of Pharmacy, Meijo University , 150 Yagotoyama, Tempaku-ku, Nagoya 468-8503, Japan.
authors.forename: Kumiko
authors.initials: K
authors.lastname: Nakamura
authors.affiliation: Faculty of Pharmacy, Meijo University , 150 Yagotoyama, Tempaku-ku, Nagoya 468-8503, Japan.
authors.forename: Masato
authors.initials: M
authors.lastname: Nakano
authors.affiliation: Faculty of Pharmacy, Meijo University , 150 Yagotoyama, Tempaku-ku, Nagoya 468-8503, Japan.
authors.forename: Yuji
authors.initials: Y
authors.lastname: Mori
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry / Q000302:isolation & purification; D000440:Butanols / Q000737:chemistry*; D004141:Dinoflagellida / Q000737:chemistry*; D004987:Ethers / Q000737:chemistry*; D015394:Molecular Structure; D011714:Pyrans / Q000138:chemical synthesis* / Q000737:chemistry / Q000302:isolation & purification; D000095702:Polyether Toxins
chemical_list: D000470:Alkaloids; D000440:Butanols; D004987:Ethers; D011714:Pyrans; C000621887:4-(benzyloxy)butanol; C532303:brevisamide; D000095702:Polyether Toxins