New Oxyfunctionalization Capabilities for ω-Hydroxylases: Asymmetric Aliphatic Sulfoxidation and Branched Ether Demethylation

Article abstract of DOI:10.1021/ja00211a033

Due to inherent difficulties in the chemical generation of aliphatic synthons, the stereo- and regioselective oxyfunctionalization of simple aliphatic substrates represents an area where chemical applications of biocatalysis would be particularly useful.The hydrocarbon monooxygenase from Pseudomonas oleovorans is a prototypical "ω-hydroxylase" known to carry out hydroxylation at the terminal methyl of alkanes as well as epoxidation of terminal olefins.It is now demonstrated that this enzyme system catalyzes stereoselective sulfoxidation of methyl thioether substrates, representing the first clear example of oxygenase-produced chiral aliphatic sulfoxides yet reported.In addition, it is shown that this enzyme system catalyzes oxygenative O-demethylation of branched alkyl methyl and branched vinyl methyl ethers to secondary alcohols and ketones, respectively.These findings establish new oxyfunctionalization capabilities, and thus a significantly expanded biotechnological potential, for the hydrocarbon monooxygenases.