TETRAHEDRON
LETTERS
Tetrahedron Letters 39 (1998) 943-946
Pergamon
Oxidative Coupling of 4-Substituted 2-Methoxy Phenols Using Methyltributylammonium
Permanganate in Dichloromethane-
Francisco A. Marque**, Fabio Simonelli, Alfredo R. M. Oliveira, George L Gohr and Paulo C. Leal
Departamento de Quimica, Universidade Federal do Paran~, C.P. 19081, BRASIL.
Received 13 October 1997; accepted 10 November 1997
Abstract: Dimers of 4-substituted 2-methoxy phenols were prepared using
methyltributylammonium permanganate (MTBAP) in dichloromethane. This
methodology allows the selective coupling of such compounds preserving other
moieties easily oxidized by permanganate anion in aqueous solution.
© 1998 ElsevierScienceLtd. All fightsreserved.
One of the chemical properties of phenols is their facile oxidation, which can be
accomplished with almost any oxidant leading to quinones, or to dimeric, trimeric or polymeric
coupling products1,2. Not only are these reactions of synthetic importance, but they are also
implicated in many biogenetic pathways3,4, 5, including the biosynthesis of lignoids.
More than two hundred of the lignoids recorded in the literature are described to have
antibiotic, antihepatotoxic, antioxidant, anti-PAF (platelet activating-factor) antitumoral, calcium
antagonistic, cytostatic, cytotoxic and enzyme inhibitor activity6.
In this work we have studied the oxidative coupling of 4-substituted 2-methoxy phenols
using methyltributylammonium permanganate (MTBAP) in dichloromethane. It has been reported 7
that the permanganate anion exhibits a lower oxidizing power in organic solvents compared with in
aqueous solution. This behaviour was exploited to effect selective oxidations of phenols bearing
other moieties easily oxidized by permanganate anion under other conditions.
This reaction led to the formation of the dimeric products whose structures, in the case of
dimers 5, 6 and 7, resemble the structures of lignoids.
0040-4039/98/$19.00 © 1998 Elsevier ScienceLtd. All fights reserved.
PIh S0040-4039(97)10665-7