The First Recyclable Molecular Ferroelectric Can Catalyze Difunctionalization of Olefin

Abstract Ferroelectrics have great potential for applications in catalysis due to their spontaneous polarization. Despite the advantages of molecular ferroelectrics in contrast to inorganic ferroelectric catalysts, molecular ferroelectric catalysis has been rarely investigated. The difunctionalization of alkenes is widely used in organic chemistry to construct complex molecules, while its conventional synthesis methods tend to be poorly selective or require harsh reaction conditions and the catalysts suffer from limited durability. Here, for the first time, molecular ferroelectric TMCM‐CdCl 3 (TMCM = Me 3 NCH 2 Cl) is used as a catalyst for the hydroxysulfurization of aryl olefins under ultrasonic stimulation, which shows high reaction selectivity, ultrahigh atom utilization, and good yield. Meanwhile, the substrates needed for this strategy are cheap and readily available, such as non‐activated olefins and thiophenols without pre‐functionalization and the green reagent oxygen from the air. More importantly, TMCM‐CdCl 3 catalyst can be easily recycled from an aqueous solution to maintain its ferroelectric and catalytic performance after 50 cycles, showing long‐term durability. The surface of TMCM‐CdCl 3 ferroelectric domains released charges under ultrasound, promoting the hydroxyl sulphation reaction. It is known that this is the first report of recyclable molecular ferroelectric‐catalyzed olefin difunctionalization, which opens up a new pathway for catalytic difunctionalization of olefin.