title: A unified route to the welwitindolinone alkaloids: total syntheses of (-)-N-methylwelwitindolinone C isothiocyanate, (-)-N-methylwelwitindolinone C isonitrile, and (-)-3-hydroxy-N-methylwelwitindolinone C isothiocyanate.
abstract: As part of a comprehensive strategy to the welwitindolinone alkaloids possessing a bicyclo[4.3.1]decane core, we report herein concise asymmetric total syntheses of (-)-N-methylwelwitindolinone C isothiocyanate (2a), (-)-N-methylwelwitindolinone C isonitrile (2b), and (-)-3-hydroxy-N-methylwelwitindolinone C isothiocyanate (3a) from a common tetracyclic intermediate. The crucial vinyl chloride moiety was installed through electrophilic chlorination of a hydrazone, but only after adjustment of reactivity to circumvent a facile skeletal rearrangement. Selective desulfurization and oxidation of 2a provided access to 2b and 3a, respectively. Notably, this work provides corrected (1)H and (13)C NMR spectral data for 3a.
authors.affiliation: Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, USA.
authors.forename: Kevin M
authors.initials: KM
authors.lastname: Allan
authors.forename: Kenichi
authors.initials: K
authors.lastname: Kobayashi
authors.forename: Viresh H
authors.initials: VH
authors.lastname: Rawal
mesh_terms: D000458:Cyanobacteria / Q000737:chemistry; D026121:Indole Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013861:Thiocyanates / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D026121:Indole Alkaloids; C092268:N-methylwelwitindolinone C isothiocyanate; D009570:Nitriles; D013861:Thiocyanates; C031760:thiocyanate