Arene hydroxylation fungi

The NIH shift has been found to occur during aromatic hydroxylations catalyzed by enzymes present in plants, animals, fungi and bacteria. It is thus evident that the acid catalyzed (or spontaneous) isomerization of oxepins-arene oxides is a very important type of in vivo reaction. It should be emphasized that the NIH shift may occur under either acid-catalyzed or neutral (spontaneous) conditions (76ACR378). The direct chemical oxidation of aromatic rings has also yielded both phenols (obtained via the NIH shift) and arene oxides (80JCS(P1)1693>. 

Fungi appear to p>referentially ortho-hydroxylate monosubstituted arenes, however there are some exceptions. For example, the near ubiquitous ftmgus Beauveria sulfiirescens (ATCC 7159) will hydroxy-late the herbicide Propham (103) to give a 49% yield of para-substituted products (104 equation 37), about half of which were (7-glycosated. 

---