Asymmetric Biomimetic Oxidations of Phenols: The Mechanism of the Diastereo- and Enantioselective Synthesis of Thomasidioic Acid

Molecules

Luca Zoia²  Maurizio Bruschi²  Marco Orlandi¹  Eeva-Liisa Tolppa² 

[1] Department of Environmental Sciences, University of Milan, Piazza della Scienza, 1, 20126 Milan, Italy; E-mails

关键词: Diastereoselection;    enantioselection;    lignans;    horseradish peroxidase;    oxidative phenol coupling;    conformational analysis;    semiempiric calculations;   

DOI  :  10.3390/molecules13010129

来源: mdpi

【 摘 要 】

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 β-β oxidative coupling step, while the diastereoselectivity is controlled by the stability of the reactive conformation of the intermediate quinomethide.

【 授权许可】

Unknown   
© 2008 by MDPI (http://www.mdpi.org).