Synthesis of the tagetitoxin core via photo-Stevens rearrangement.
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.
Mortimer
Anne J Price
AJ
Department of Chemistry, University College London, Christopher Ingold Building, 20 Gordon Street, London WC1H 0AJ, UK.
Aliev
Abil E
AE
Tocher
Derek A
DA
Porter
Michael J
MJ
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
D003998:Dicarboxylic Acids; D004791:Enzyme Inhibitors; D009943:Organophosphorus Compounds; D013455:Sulfur; C062221:tagetitoxin; D012321:DNA-Directed RNA Polymerases