Molecules (Jan 2008)

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

  • Bruno Rindone,
  • Eeva-Liisa Tolppa,
  • Marco Orlandi,
  • Maurizio Bruschi,
  • Luca Zoia

DOI
https://doi.org/10.3390/molecules13010129
Journal volume & issue
Vol. 13, no. 1
pp. 129 – 148

Abstract

Read online

Enantiopure chiral amidic derivatives of sinapic acid were oxidised withhydrogen peroxide using horseradish peroxidase (HRP) as the catalyst to give thearyltetraline dilignol thomasidioic acid. Trans-diastereoselectivity and enantioselectivity inthe formation of thomasidioic acid was observed. Computational methods show that theenantioselectivity is controlled by the β-β oxidative coupling step, while thediastereoselectivity is controlled by the stability of the reactive conformation of theintermediate quinomethide.

Keywords