title: Synthesis of resveratrol tetramers via a stereoconvergent radical equilibrium.
abstract: Persistent free radicals have become indispensable in the synthesis of organic materials through living radical polymerization. However, examples of their use in the synthesis of small molecules are rare. Here, we report the application of persistent radical and quinone methide intermediates to the synthesis of the resveratrol tetramers nepalensinol B and vateriaphenol C. The spontaneous cleavage and reconstitution of exceptionally weak carbon-carbon bonds has enabled a stereoconvergent oxidative dimerization of racemic materials in a transformation that likely coincides with the biogenesis of these natural products. The efficient synthesis of higher-order oligomers of resveratrol will facilitate the biological studies necessary to elucidate their mechanism(s) of action.
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, MI 48109, USA.
authors.forename: Mitchell H
authors.initials: MH
authors.lastname: Keylor
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, MI 48109, USA.
authors.forename: Bryan S
authors.initials: BS
authors.lastname: Matsuura
authors.affiliation: Department of Chemistry and Biomolecular Sciences, University of Ottawa, 10 Marie Curie Private,Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Markus
authors.initials: M
authors.lastname: Griesser
authors.affiliation: Department of Chemistry and Biomolecular Sciences, University of Ottawa, 10 Marie Curie Private,Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Jean-Philippe R
authors.initials: JR
authors.lastname: Chauvin
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, MI 48109, USA.
authors.forename: Ryan A
authors.initials: RA
authors.lastname: Harding
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, MI 48109, USA.
authors.forename: Mariia S
authors.initials: MS
authors.lastname: Kirillova
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, MI 48109, USA.
authors.forename: Xu
authors.initials: X
authors.lastname: Zhu
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, MI 48109, USA.
authors.forename: Oliver J
authors.initials: OJ
authors.lastname: Fischer
authors.affiliation: Department of Chemistry and Biomolecular Sciences, University of Ottawa, 10 Marie Curie Private,Ottawa, Ontario K1N 6N5, Canada. crjsteph@umich.edu dpratt@uottawa.ca.
authors.forename: Derek A
authors.initials: DA
authors.lastname: Pratt
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, MI 48109, USA. crjsteph@umich.edu dpratt@uottawa.ca.
authors.forename: Corey R J
authors.initials: CR
authors.lastname: Stephenson
mesh_terms: D001572:Benzofurans / Q000138:chemical synthesis*; D001688:Biological Products / Q000138:chemical synthesis*; D002244:Carbon / Q000737:chemistry; D019281:Dimerization; D045563:Indolequinones / Q000737:chemistry*; D010084:Oxidation-Reduction; D012118:Resorcinols / Q000138:chemical synthesis*; D000077185:Resveratrol; D013267:Stilbenes / Q000138:chemical synthesis*
chemical_list: D001572:Benzofurans; D001688:Biological Products; D045563:Indolequinones; D012118:Resorcinols; D013267:Stilbenes; C068040:quinone methide; D002244:Carbon; D000077185:Resveratrol