Asymmetric biomimetic oxidations of phenols: the mechanism of the diastereo- and enantioselective synthesis of thomasidioic acid.
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.
Zoia
Luca
L
Department of Environmental Sciences, University of Milan, Piazza della Scienza, 1, 20126 Milan, Italy.
Bruschi
Maurizio
M
Orlandi
Marco
M
Tolppa
Eeva-Liisa
EL
Rindone
Bruno
B
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
D001565:Benzoates; D001713:Biphenyl Compounds; D005663:Furans; D017705:Lignans; D010636:Phenols; C475898:thomasidioic acid; C103298:pinoresinol