Immobilization of Unspecific Peroxygenase for Selective Oxidation of Diols

Diols are versatile starting materials for preparing a series of value-added products. However, the biocatalytic oxidation of diols to hemiacetals remains challenging, primarily due to the inherent instability of hemiacetals in aqueous media. Herein, we report the use of unspecific peroxygenases for the mild and selective oxidation of diols into hemiacetal products. Based on the concept of reaction engineering, this catalytic process was performed under neat reaction condition using immobilized enzymes. This unique reaction system allowed a variety of patterned diols being converted into the stable hemiacetal products with chemoselectivity up to 99%. By optimizing the reaction conditions, the hemiacetal products were converted in situ to lactones, thereby further broadening the application of diol oxidation reactions. The molecular modeling of the enzyme-substrate interaction sets up a basis for the mechanistic understanding of the reaction activity and selectivity. This work demonstrated a new approach of transforming diols into synthetic building blocks by unspecific peroxygenases.