SELECTIVITY OF THE BIOOXYGENATION OF N-PHENYLCARBAMATES BY THE FUNGUSBEAUVERIA-BASSIANA

The biotransformation with Beauveria bassiana of 5-dimethylbicyclo[3.2 .1]oct-8-yl-N-phenylcarbamate (11), its anti-isomer 13 and cyclooctyl- N-phenylcarbamate 31 is described. Based on the observed hydroxylation positions and on earlier results of oxygenations using this fungus, a modified distance model for hydroxylations is proposed. The mode of b inding of the substrate to the enzyme's active site depends on the int rinsic structure and electronic properties of its electron-rich group. The regio-and stereochemistry of hydroxylation, however, is determine d mainly by the structure of the hydrocarbon moiety, namely by a speci fic gap from the anchoring group. This is represented by a distance of about 5.5 Angstrom between the oxygen directly attached to the carboc ycle and hydrogens which potentially can be substituted. (C) 1997 Else vier Science Ltd.