Enzymic Baeyer–Villiger Oxidations by Flavin‐Dependent Monooxygenases

TLDR

Microbial biochemistry has gained renewed interest because of the prevalence of xenobiotic compounds and advances in genetic engineering, and the Baeyer–Villiger reaction—though valuable for converting ketones to esters or lactones—often suffers from low yields and harsh conditions. The study identifies bacteria that grow on aliphatic molecules and possess enzymes capable of catalyzing Baeyer–Villiger reactions. These enzymes are monooxygenases that catalyze Baeyer–Villiger reactions on aliphatic ketones. The enzymes exhibit a remarkable range of Baeyer–Villiger reactions, and their availability in pure form via genetic engineering suggests they could serve as useful reagents in organic synthesis.

Abstract

Abstract There has recently been a revival of interest in microbial biochemistry. Part of this resurgence is due to the increased presence of man‐made organic compounds in the biosphere and the resultant interest in microorganisms which can degrade these xenobiotic molecules. Also, advances in genetic engineering have raised the possibility of utilizing the chemical machinery of bacteria for commercial profit and social benefit. The Baeyer‐Villiger reaction is a useful transformation in organic synthesis which provides chemists with a gentle means of converting ketones into esters or lactones. The reaction, however, suffers from the problems of low yield and the need, in some cases, to utilize harsh conditions. There exist bacteria, capable of growth on aliphatic molecules, that contain enzymes which can catalyze Baeyer‐Villiger reactions. These enzymes, known as monooxygenases, are involved in the breakdown of acyclic and alicyclic ketones to provide simpler carbon units for further catabolism. The gamut of reactions catalyzed by some of these enzymes is remarkable. This diversity, plus their availability in pure form in quantity by genetic engineering raises the possibility that these biocatalysts can be useful as reagents in organic synthesis.