title: Asymmetric biomimetic oxidations of phenols: the mechanism of the diastereo- and enantioselective synthesis of thomasidioic acid.
abstract: Enantiopure chiral amidic derivatives of sinapic acid were oxidised with hydrogen peroxide using horseradish peroxidase (HRP) as the catalyst to give the aryltetraline dilignol thomasidioic acid. Trans-diastereoselectivity and enantioselectivity in the formation of thomasidioic acid was observed. Computational methods show that the enantioselectivity is controlled by the beta-beta oxidative coupling step, while the diastereoselectivity is controlled by the stability of the reactive conformation of the intermediate quinomethide.
authors.affiliation: Department of Environmental Sciences, University of Milan, Piazza della Scienza, 1, 20126 Milan, Italy.
authors.forename: Luca
authors.initials: L
authors.lastname: Zoia
authors.forename: Maurizio
authors.initials: M
authors.lastname: Bruschi
authors.forename: Marco
authors.initials: M
authors.lastname: Orlandi
authors.forename: Eeva-Liisa
authors.initials: EL
authors.lastname: Tolppa
authors.forename: Bruno
authors.initials: B
authors.lastname: Rindone
mesh_terms: D001565:Benzoates / Q000138:chemical synthesis* / Q000737:chemistry*; D032701:Biomimetics / Q000379:methods*; D001713:Biphenyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D005663:Furans / Q000737:chemistry; D006868:Hydrolysis; D017705:Lignans / Q000737:chemistry; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010636:Phenols / Q000378:metabolism*; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D001565:Benzoates; D001713:Biphenyl Compounds; D005663:Furans; D017705:Lignans; D010636:Phenols; C475898:thomasidioic acid; C103298:pinoresinol