Photoelectrochemical Tandem Chlorination of sp<sup>3</sup> C–H Bond in Seawater/Chloroform Two-Phase Electrolyte System by Ti-Doped Fe<sub>2</sub>O<sub>3</sub> Photoanode
Sang Youn Chae, Adeel Mehmood, Eun Duck Park
Abstract
C–H bond activation is a fundamental challenge in organic synthesis, and various routes have been explored. Among them, halogenation has played an important role in producing valuable intermediates. We report a novel photoelectrochemical (PEC) tandem C–H chlorination using a Ti-doped Fe 2 O 3 (Ti:Fe 2 O 3 ) photoanode in a two-phase electrolyte system consisting of natural seawater and a chloroform organic phase. This system enables the in situ generation of Cl 2 via the chlorine evolution reaction (CER) with near 100% Faradaic efficiency (FE) while suppressing the competing oxygen evolution reaction (OER). The generated Cl 2 undergoes photolytic cleavage, forming chlorine radicals that selectively chlorinate sp 3 C–H bonds in toluene, cyclohexane, and ethylbenzene with 100% regioselectivity. This work demonstrates the feasibility of seawater-based PEC halogenation and provides a sustainable strategy for selective C–H functionalization in organic synthesis.