title: A biomimetic approach to the rocaglamides employing photogeneration of oxidopyryliums derived from 3-hydroxyflavones.
abstract: A unified biomimetic approach to the aglain-forbaglin-rocaglamide classes of natural products is reported. The approach involves photogeneration of oxidopyryliums via excited-state intramolecular proton transfer (ESIPT) of 3-hydroxyflavones followed by [3+2] dipolar cycloaddition to the aglain core. An alpha-ketol (acyloin) rearrangement was employed to transform the aglain core to the rocaglamide framework. This approach was successfully used for the synthesis of the natural product (+/-)-methyl rocaglate.
authors.affiliation: Department of Chemistry, Center for Chemical Methodology and Library Development, Boston University, Boston, Massachusetts 02215, USA.
authors.forename: Baudouin
authors.initials: B
authors.lastname: Gerard
authors.forename: Guilford
authors.initials: G
authors.lastname: Jones Ii
authors.forename: John A
authors.initials: JA
authors.lastname: Porco
mesh_terms: D001572:Benzofurans / Q000138:chemical synthesis* / Q000378:metabolism; D040761:Biomimetic Materials / Q000138:chemical synthesis / Q000378:metabolism; D005419:Flavonoids / Q000737:chemistry* / Q000378:metabolism; D010777:Photochemistry; D011726:Pyridinium Compounds / Q000737:chemistry* / Q000378:metabolism
chemical_list: D001572:Benzofurans; D005419:Flavonoids; D011726:Pyridinium Compounds; C107772:rocaglamide; C041477:3-hydroxyflavone