title: Evolution of a synthetic strategy: total synthesis of (+/-)-welwitindolinone A isonitrile.
abstract: An efficient and highly stereoselective total synthesis of the natural product (+/-)-welwitindolinone A isonitrile (1) is described. The bicyclo[4.2.0]octane core of 1 was established by a regio- and diastereoselective [2+2] ketene cycloaddition. The C12 quaternary center and vicinal stereogenic chlorine were installed in a single operation with excellent stereocontrol via a chloronium ion mediated semipinacol rearrangement. Described strategies for construction of the spiro-oxinole include a SmI2-LiCl mediated reductive cyclization and a novel anionic cyclization that simultaneously constructs the spiro-oxindole and vinyl isonitrile moieties.
authors.affiliation: Sterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, USA.
authors.forename: Sarah E
authors.initials: SE
authors.lastname: Reisman
authors.forename: Joseph M
authors.initials: JM
authors.lastname: Ready
authors.forename: Matthew M
authors.initials: MM
authors.lastname: Weiss
authors.forename: Atsushi
authors.initials: A
authors.lastname: Hasuoka
authors.forename: Makoto
authors.initials: M
authors.lastname: Hirata
authors.forename: Kazuhiko
authors.initials: K
authors.lastname: Tamaki
authors.forename: Timo V
authors.initials: TV
authors.lastname: Ovaska
authors.forename: Catherine J
authors.initials: CJ
authors.lastname: Smith
authors.forename: John L
authors.initials: JL
authors.lastname: Wood
mesh_terms: D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D003500:Cyclization; D026121:Indole Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D007211:Indoles / Q000138:chemical synthesis / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry; D008968:Molecular Conformation; D009795:Octanes / Q000737:chemistry*; D013141:Spiro Compounds / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D001643:Bridged Bicyclo Compounds; D026121:Indole Alkaloids; D007211:Indoles; D007659:Ketones; D009795:Octanes; D013141:Spiro Compounds; C527897:welwitindolinone A isonitrile