title: Total synthesis of (±)-gephyrotoxin by amide-selective reductive nucleophilic addition.
abstract: A chemoselective approach for the total synthesis of (±)-gephyrotoxin has been developed. The key to success was the utilization of N-methoxyamides, which enabled the direct coupling of the amide with an aldehyde and selective reductive nucleophilic addition to the amide in the presence of a variety of sensitive and electrophilic functional groups, such as a methyl ester. This chemoselective approach minimized the use of protecting-group manipulations and redox reactions, which resulted in the most concise and efficient total synthesis of (±)-gephyrotoxin described to date.
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan).
authors.forename: Kenji
authors.initials: K
authors.lastname: Shirokane
authors.forename: Takamasa
authors.initials: T
authors.lastname: Wada
authors.forename: Makoto
authors.initials: M
authors.lastname: Yoritate
authors.forename: Ryo
authors.initials: R
authors.lastname: Minamikawa
authors.forename: Nobuaki
authors.initials: N
authors.lastname: Takayama
authors.forename: Takaaki
authors.initials: T
authors.lastname: Sato
authors.forename: Noritaka
authors.initials: N
authors.lastname: Chida
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D000577:Amides / Q000737:chemistry*; D002384:Catalysis; D008698:Mesylates / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D012538:Scandium / Q000737:chemistry; D013237:Stereoisomerism; D014220:Trialkyltin Compounds / Q000737:chemistry
chemical_list: D000470:Alkaloids; D000577:Amides; D008698:Mesylates; D014220:Trialkyltin Compounds; C436603:scandium triflate; C014569:gephyrotoxin; C011559:tributyltin; D012538:Scandium
keywords: amides; chemoselectivity; gephyrotoxin; nucleophilic addition; total synthesis