title: Inter- and intramolecular reactions of 1-deoxy-1-thio-1,6-anhydrosugars with α-diazoesters: synthesis of the tagetitoxin core by photochemical ylide rearrangement.
abstract: The one-carbon ring expansion of 1-deoxy-1-thio-1,6-anhydrosugars, mediated by metal carbenes and proceeding through the intermediacy of sulfur ylides, has been proposed as a route for the synthesis of the tagetitoxin skeleton. Intermolecular reactions of such thioanhydrosugars with diazoesters afford a range of undesired products derived from the initially formed ylide, whereas use of an intramolecular process generates stable ylides which can be converted to the tagetitoxin skeleton by photo-Stevens rearrangement. Computational studies using density functional theory indicate that the photochemical rearrangement likely proceeds through a homolysis-recombination pathway.
authors.affiliation: Department of Chemistry, University College London, Christopher Ingold Building, 20 Gordon Street, London, WC1H 0AJ, UK.
authors.forename: Anne J
authors.initials: AJ
authors.lastname: Price Mortimer
authors.forename: Julien R H
authors.initials: JR
authors.lastname: Plet
authors.forename: Oluwafunsho A
authors.initials: OA
authors.lastname: Obasanjo
authors.forename: Nikolas
authors.initials: N
authors.lastname: Kaltsoyannis
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Porter
mesh_terms: D001391:Azo Compounds / Q000737:chemistry*; D003998:Dicarboxylic Acids / Q000138:chemical synthesis* / Q000737:chemistry; D004952:Esters / Q000737:chemistry*; D015394:Molecular Structure; D009844:Oligosaccharides / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D055668:Photochemical Processes; D011789:Quantum Theory; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D001391:Azo Compounds; D003998:Dicarboxylic Acids; D004952:Esters; D009844:Oligosaccharides; D009943:Organophosphorus Compounds; D013438:Sulfhydryl Compounds; C062221:tagetitoxin