Recent development of biomimetic halogenation inspired by vanadium dependent haloperoxidase

Organohalide is one of the most important and useful compounds in organic chemistry, broadly embodied in diverse bioactive molecules, organic materials and agrochemicals. Installation of halide to organic compound, in most cases, still relies on traditional electrophilic halogenation (e.g., utilizing Br-2, I-2 and Cl-2), particularly in industrial production. Such process unavoidably generates undesired environmentally unfriendly by-products (e.g., HBr from Br-2). By contrast, in nature the haloperoxidase produces organic halides under mild condition in atom economy. But they suffer from high cost, limited substrate scope and specific working condition. The biomimetic halogenation inspired by nature, in theory, provides a potential solution for these limitations, serving as an alternative green halogenation approach. In this review, the author summarized the recent development of biomimetic halogenation inspired by vanadium dependent haloperoxidase (VHPO). Evident progress has been achieved in its functional mimics utilizing transition metal (TM) catalysts, including vanadate (V5+), molybdate (Mo6+), tungstate (W6+), and rhenate (Re7+). These robust biomimetic catalysts work efficiently under mild condition with broad substrate scope, and even afforded drug molecules in preparative scale. The challenges and opportunities for further development in this field were also discussed, along with the elucidation of VHPO's structure, functional mechanism and synthetic application. (c) 2022 Elsevier B.V. All rights reserved.

Automated summary

Organohalides are important and useful compounds in organic chemistry, but their traditional halogenation methods generate environmentally unfriendly by-products. Biomimetic halogenation inspired by nature offers a green alternative. This review summarizes the recent progress of biomimetic halogenation using vanadium-dependent haloperoxidase, discussing its challenges, opportunities, and synthetic applications.