Synthesis of Layered Copper‐Based 2D‐MOFs for Enhanced Catalytic Regioselective Phosphorylation of Alkynes and P−H Bonds

Abstract

A functionalized heterogeneous Cu‐based metal‐organic framework (Cu‐2D‐MOF) was synthesized through the reaction of Cu(NO₃)₂ ⋅ 3H₂O with 2,3,5,6‐tetrafluoroterephthalic acid and 4,4′‐bipyridine. The synthesized material underwent comprehensive characterization using various techniques, including FT‐IR spectroscopy, N₂ physical adsorption, scanning electron microscopy (SEM), and X‐ray photoelectron spectroscopy (XPS). Subsequently, the catalytic performance of Cu‐2D‐MOFs was assessed in the hydrophosphorylation and aerobic oxidative dehydrogenative coupling reactions involving alkynes and P−H bonds. The catalyst demonstrated remarkable catalytic activity in both transformations, effectively yielding a wide variety of (E)‐alkenyl‐phosphoryl and alkynyl‐phosphoryl compounds, respectively. Notably, the incorporation of this MOF material facilitated the phosphorylation reaction to proceed seamlessly, eliminating the necessity for supplementary small molecular organic ligands. Furthermore, the catalyst demonstrated ease of recovery and recyclability through a simple recovery process. Employing a systematic approach of sequential control experiments, we have delineated the potential transformation pathway of the reaction and consequently hypothesized a probable reaction mechanism for the observed transformation.