Biocatalytic Cross-Coupling of Aryl Halides with a Genetically Engineered Photosensitizer Artificial Dehalogenase

Devising artificial photoenzymes for abiological bond-forming reactions is of high synthetic value but also a tremendous challenge. Disclosed herein is the first photobiocatalytic cross-coupling of aryl halides enabled by a designer artificial dehalogenase, which features a genetically encoded benzophenone chromophore and site-specifically modified synthetic Ni-II(bpy) cofactor with tunable proximity to streamline the dual catalysis. Transient absorption studies suggest the likelihood of energy transfer activation in the elementary organometallic event. This design strategy is viable to significantly expand the catalytic repertoire of artificial photoenzymes for useful organic transformations.

Automated summary

This study successfully achieved the photobiocatalytic cross-coupling of aryl halides using a designer artificial dehalogenase, demonstrating high synthetic value. The research results suggest the optimization of dual catalysis through a genetically encoded chromophore and site-specific modified cofactor, potentially expanding the catalytic repertoire of artificial photoenzymes for various organic transformations.