Asymmetric diphenol formation by a fungal laccase.

A laccase isolated from the fungus Rhizoctonia praticola catalyzed the cross-coupling of two differently halogenated phenols. When 2,4-dichlorophenol and 4-bromo-2-chlorophenol were incubated together with the enzyme, three dimers were formed and isolated by thin-layer chromatography. The molecular weights of these compounds were determined by mass spectrometry as 322, 410, and 366, which correspond with the respective dimers of each of the phenols and with a hybrid formed from both, tentatively assigned the structure 3,3',5'-trichloro-5-bromo-2,2'-diphenol. Gas chromatography-mass spectrometry analysis of these products and of their methylated derivatives lent support to these structural assignments.