Stereo- and regioselectivity in the P450-catalyzed oxidative tandem difunctionalization of 1-methylcyclohexene

The selective partial oxidation of small non-functionalized molecules using biocatalysis based on P450 monooxygenases is known to be difficult due to the expected poor regio- and stereoselectivity, but in this study it was nevertheless attempted. 1-Methylcyclohexene was subjected to oxygen-mediated biocatalytic oxidation using P450-BM3 as the catalyst. Both oxidative hydroxylation and epoxidation were observed, in some cases leading to hydroxy epoxides with high diastereo- and enantioselectivity especially when employing BM3 mutants.