title: Sequential Ketene Generation from Dioxane-4,6-dione-keto-dioxinones for the Synthesis of Terpenoid Resorcylates.
abstract: Trapping of the ketene generated from the thermolysis of 2-methyl-2-phenyl-1,3-dioxane-4,6-dione-keto-dioxinone at 50 °C with primary, secondary, or tertiary alcohols gave the corresponding dioxinone β-keto-esters in good yield under neutral conditions. These intermediates were converted by palladium(0)-catalyzed decarboxylative allyl migration and aromatization into the corresponding β-resorcylates. These transformations were applied to the syntheses of the natural products (±)-cannabiorcichromenic and (±)-daurichromenic acid.
authors.affiliation: Department of Chemistry, Imperial College , London, SW7 2AZ, U.K.
authors.forename: Daniel C
authors.initials: DC
authors.lastname: Elliott
authors.affiliation: Department of Chemistry, Imperial College , London, SW7 2AZ, U.K.
authors.forename: Tsz-Kan
authors.initials: TK
authors.lastname: Ma
authors.affiliation: Department of Chemistry, Imperial College , London, SW7 2AZ, U.K.
authors.forename: Aymane
authors.initials: A
authors.lastname: Selmani
authors.affiliation: Department of Chemistry, Imperial College , London, SW7 2AZ, U.K.
authors.forename: Rosa
authors.initials: R
authors.lastname: Cookson
authors.affiliation: Department of Chemistry, Imperial College , London, SW7 2AZ, U.K.
authors.forename: Philip J
authors.initials: PJ
authors.lastname: Parsons
authors.affiliation: Department of Chemistry, Imperial College , London, SW7 2AZ, U.K.
authors.forename: Anthony G M
authors.initials: AG
authors.lastname: Barrett
mesh_terms: D001578:Benzopyrans / Q000138:chemical synthesis* / Q000737:chemistry; D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D002839:Chromans / Q000138:chemical synthesis* / Q000737:chemistry; D004146:Dioxanes / Q000737:chemistry*; D005030:Ethylenes / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism; D013729:Terpenes / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: C000611008:2-methyl-2-phenyl-1,3-dioxane-4,6-dione-keto-dioxinone; D001578:Benzopyrans; D001688:Biological Products; D002839:Chromans; D004146:Dioxanes; D005030:Ethylenes; D007659:Ketones; D013729:Terpenes; C489925:daurichromenic acid; D010165:Palladium; C090972:cannabiorcichromenic acid; C008223:ketene