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

Inspired by natural cryptic halogenation in -bond formation, this study developed a synthetic approach combining biocatalytic bromination with transition-metal-catalyzed cross-coupling. Using the cyanobacterial 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.