Chemoenzymatic C,C-Bond Forming Cascades by Cryptic Vanadium Haloperoxidase Catalyzed Bromination

Inspired by natural cryptic halogenation in <i>C,C</i>-bond formation, this study developed a synthetic approach combining biocatalytic bromination with transition-metal-catalyzed cross-coupling. Using the cyanobacterial <i>Am</i>VHPO, a robust and sustainable bromination-arylation cascade was created. Genetic modifications allowed enzyme immobilization, enhancing the compatibility between biocatalysis and chemocatalysis. This mild, efficient method for synthesizing biaryl compounds provides a foundation for future biochemo cascade reactions harnessing halogenation as a traceless directing tool.