Gram-Scale Synthesis of Heterogeneous Cu-MOFs Catalyst with Dual Functionalities for Late-stage Dicarbofunctionalization of Alkenes

Abstract

Multifunctional catalysts in organic synthesis are highly attractive, particularly in the construction of complex molecules. Here, we report the first example of heterogeneous Cu-MOFs catalyst with dual functions of photoredox and cross-coupling. IMU-108 can be synthesized on a gram scale from Cu(NO₃)₂·3H₂O and 5-mercaptoisophthalic acid precursors by a simple reflux process. X-ray diffraction results revealed that IMU-108 is constructed from the in-situ bridged S-S bond between the zero-dimension metal-organic polyhedra (MOPs). The inter-polyhedras S-S bonds not only create a rigid geometric structure, but also allow IMU-108 to be bench-stable, while still maintaining excellent catalysis. We demonstrate the capacity of IMU-108 in heterogeneous photoredox-catalyzed cross-coupling of styrenes, α-carbonyl alkyl and bromides with boronic acids to yield various substituted 1,1-diarylalkanes in a single step. The versatility of this method enables late-stage functionalization of complex molecules without the need for de novo synthesis. Moreover, IMU-108 exhibits good recyclability, maintaining its catalytic activity over six consecutive reaction cycles.