Chemoenzymatic Decarboxylative Bromination of Acetylenic Acids Using Vanadium-Dependent Chloroperoxidase
Zhigang Zeng, Richa Hu, Jianqun Peng, Yufei Liu, Huanhuan Li, Wuyuan Zhang
Abstract
Haloalkynes are versatile building blocks in organic transformations. However, the traditional synthesis of these compounds, using either Br 2 or N -bromosuccinimide, suffers from significant waste generation. Herein, we use vanadium-dependent chloroperoxidase from Curvularia inaequalis ( Ci VCPO) for the in situ generation of reactive hypobromite, which enables the chemoenzymatic decarboxylation bromination of phenylpropiolic acids. A broad range of substrates were converted into the corresponding haloalkynes in up to 99% conversion and 99% chemoselectivity. This method was also cascaded with chemocatalysis to yield various important building blocks. This work not only reports a mild and environmentally friendly alternative to prepare the versatile haloalkynes but also expands the oxidation chemistry of vanadium-dependent chloroperoxidases.