title: Total synthesis of (+)-sarain A.
abstract: This article describes the details of our synthetic studies toward the complex marine alkaloid sarain A. Various strategies were conceived, setbacks encountered, and solutions developed, ultimately leading to a successful enantioselective total synthesis. Our route to (+)-sarain A features a number of key steps, including an asymmetric Michael addition to install the C4'-C3'-C7' stereotriad, an enoxysilane-N-sulfonyliminium ion cyclization to set the C3 quaternary carbon stereocenter, and assemble the diazatricycloundecane core, a ring-closing metathesis to construct the 13-membered ring, an intramolecular Stille coupling to fashion the unsaturated 14-membered macrocycle, and a late-stage installation of the tertiary amine-aldehyde proximity interaction.
authors.affiliation: Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, California 92697-2025, USA.
authors.forename: Michael H
authors.initials: MH
authors.lastname: Becker
authors.forename: Peter
authors.initials: P
authors.lastname: Chua
authors.forename: Robert
authors.initials: R
authors.lastname: Downham
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Douglas
authors.forename: Neil K
authors.initials: NK
authors.lastname: Garg
authors.forename: Sheldon
authors.initials: S
authors.lastname: Hiebert
authors.forename: Stefan
authors.initials: S
authors.lastname: Jaroch
authors.forename: Richard T
authors.initials: RT
authors.lastname: Matsuoka
authors.forename: Joy A
authors.initials: JA
authors.lastname: Middleton
authors.forename: Fay W
authors.initials: FW
authors.lastname: Ng
authors.forename: Larry E
authors.initials: LE
authors.lastname: Overman
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis / Q000737:chemistry; D000473:Alkanes / Q000138:chemical synthesis; D000818:Animals; D001952:Bridged-Ring Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D003500:Cyclization; D008958:Models, Molecular; D011161:Porifera; D013237:Stereoisomerism
chemical_list: D000470:Alkaloids; D000473:Alkanes; D001952:Bridged-Ring Compounds; C410431:sarain A; C022884:undecane