Bifunctional Copper Metal-Organic Framework Catalyst for Late-Stage Functionalization of Alkenes

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作   者：

Dong, Lu;  Chen, Hu;  Tan, Xiaoli;  Zhang, Ning;  Sun, Wei;  Li, Dechao;  Liang, Guangchao;  Jia, Yanyuan;  Guo, Shuo; 

作者机构：

Xidian Univ;  Inner Mongolia University College of Chemistry and Chemical Engineering; 

关键词：

copper catalysis;  1,1-diaryl compounds;  heterogeneous catalysis;  late-stage functionalization;  photoredox catalysis;  metal-organic frameworks; 

期刊名称：

ACS catalysis

i s s n：

年卷期：

2025 年 15 卷 5 期

页   码：

4198-4207

页   码：

摘   要：

Multifunctional catalysts in organic synthesis are highly attractive, particularly in the construction of complex molecules. In this work, we report a heterogeneous bifunctional Cu-based metal-organic framework (MOF) catalyst, IMU-108, serving as both a photoredox catalyst and a cross-coupling catalyst. IMU-108 was synthesized on a gram scale from Cu(NO3)23H2O and 5-mercaptoisophthalic acid precursors through a simple refluxing device. The structure of IMU-108 is formed via an in situ S-S bridge bond connecting zero-dimensional metal-organic polyhedra (MOPs), each composed of 12 Cu-Cu paddle-wheel motifs. These interpolyhedral S-S bonds result in a rigid geometric structure and ensure inner MOPs remain bench-stable while maintaining catalytic activity. We demonstrate the capacity of IMU-108 in heterogeneous photoredox-catalyzed cross-coupling of styrenes and alpha-bromo esters with boronic acids to yield various substituted 1,1-diaryl alkanes in a single step. The versatility of this method enables late-stage functionalization of complex molecules without the need for de novo synthesis. IMU-108 exhibits good reusability, maintaining its catalytic activity over ten consecutive reaction cycles. Furthermore, computational and mechanistic studies suggest that coordinatively unsaturated copper species on the surface of IMU-108 served as catalytically active sites, possessing competent Single-Electron Transfer (SET) reduction ability and facilitating cross-coupling reactions.