title: Synthesis of the tagetitoxin core via photo-Stevens rearrangement.
abstract: The core structure of the RNA polymerase inhibitor tagetitoxin has been synthesized by one-carbon ring expansion of bridged bicyclic monothioacetals. The key steps are intramolecular ylide formation by reaction between the sulfur atom and a pendant diazoester, followed by an efficient photochemical 1,2-rearrangement to give the desired 9-oxa-3-thiabicyclo[3.3.1]nonane ring system.
authors.affiliation: Department of Chemistry, University College London, Christopher Ingold Building, 20 Gordon Street, London WC1H 0AJ, UK.
authors.forename: Anne J Price
authors.initials: AJ
authors.lastname: Mortimer
authors.forename: Abil E
authors.initials: AE
authors.lastname: Aliev
authors.forename: Derek A
authors.initials: DA
authors.lastname: Tocher
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Porter
mesh_terms: D012321:DNA-Directed RNA Polymerases / Q000037:antagonists & inhibitors; D003998:Dicarboxylic Acids / Q000138:chemical synthesis* / Q000737:chemistry*; D004791:Enzyme Inhibitors / Q000138:chemical synthesis* / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D055668:Photochemical Processes; D013455:Sulfur / Q000737:chemistry
chemical_list: D003998:Dicarboxylic Acids; D004791:Enzyme Inhibitors; D009943:Organophosphorus Compounds; D013455:Sulfur; C062221:tagetitoxin; D012321:DNA-Directed RNA Polymerases