title: A redox economical synthesis of bioactive 6,12-guaianolides.
abstract: Syntheses of two 6,12-guaianolide analogs are reported within. The scope of the tandem allylboration/lactonization chemistry is expanded to provide a functionalized allene-yne-containing α-methylene butyrolactone that undergoes a Rh(I)-catalyzed cyclocarbonylation reaction to afford a 5-7-5 ring system. The resulting cycloadducts bear a structural resemblance to other NF-κB inhibitors such as cumambrin A and indeed were shown to inhibit NF-κB signaling and cancer cell growth.
authors.affiliation: Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
authors.forename: Bo
authors.initials: B
authors.lastname: Wen
authors.forename: Joseph K
authors.initials: JK
authors.lastname: Hexum
authors.forename: John C
authors.initials: JC
authors.lastname: Widen
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Harki
authors.forename: Kay M
authors.initials: KM
authors.lastname: Brummond
mesh_terms: D000466:Alkadienes / Q000737:chemistry*; D002384:Catalysis; D006801:Humans; D015394:Molecular Structure; D016328:NF-kappa B / Q000037:antagonists & inhibitors* / Q000737:chemistry* / Q000378:metabolism; D010084:Oxidation-Reduction; D012238:Rhodium / Q000737:chemistry*; D045789:Sesquiterpenes, Guaiane / Q000138:chemical synthesis* / Q000737:chemistry; D015398:Signal Transduction; D013237:Stereoisomerism
chemical_list: D000466:Alkadienes; D016328:NF-kappa B; D045789:Sesquiterpenes, Guaiane; D012238:Rhodium