Chlorination of Amines by a Vanadium-Dependent Chloroperoxidase

Chloramines are an important class of compounds containing a covalent nitrogen-chlorine bond. Despite the growing interest in their applications in the small molecule and polymer industries, selective and sustainable catalyst systems for their synthesis have remained elusive. We recently discovered that the vanadium-dependent chloroperoxidase from Curvularia inaequalis (CiVCPO) is an effective biocatalyst for selective chlorination of a broad range of structurally diverse amines to give the corresponding chloramines and chlorimines in moderate to high yield and with excellent chemoselectivity. The catalyst system is readily scalable and applied to chemoenzymatic nitrile and amide synthesis. Finally, halide divergent reactivity is demonstrated in chloride-selective chlorimine formation and bromide-selective aldehyde formation using the same biocatalyst.