A Copper Metal–Organic Framework as an Efficient and Recyclable Catalyst for the Oxidative Cross‐Dehydrogenative Coupling of Phenols and Formamides

Abstract

A crystalline porous metal‐organic framework Cu2(BPDC)2(BPY) (BPDC=4,4′‐biphenyldicarboxylate, BPY=4,4′‐bipyridine) was synthesized and characterized by several techniques including XRD, SEM, TEM, thermogravimetric analysis, FTIR, atomic absorption spectrophotometry, hydrogen temperature‐programmed reduction, and nitrogen physisorption measurements. The Cu2(BPDC)2(BPY) could be employed as a heterogeneous catalyst for the copper‐catalyzed cross‐dehydrogenative coupling reaction of DMF with 2‐substituted phenols to form organic carbamates through CH activation under oxidative conditions. The Cu2(BPDC)2(BPY) offered higher catalytic activity than common copper salts such as Cu(OAc)2, CuCl, CuCl2, CuI, and Cu(NO3)2 as well as other Cu–MOFs such as Cu3(BTC)2, Cu(BDC), and Cu(BPDC). The Cu2(BPDC)2(BPY) catalyst could be facilely separated from the reaction mixture, could be recovered and reused several times without significant degradation in catalytic activity.

Direct Oxidative Amidation between N,N‐dimethylanilines and Anhydrides Using Metal‐Organic Framework [Cu2(EDB)2(BPY)] as an Efficient Heterogeneous Catalyst

“…[27][28][29] A variety of MOFs have been employed as catalysts or catalyst supports for many organic reactions, ranging from carbon-carbon [30][31][32][33] to carbon-heteroatom forming transformations. [36,[42][43][44][45][46][47][48][49] Herein, we present the direct oxidative amidation of N,N-dimethylanilines with anhydrides using the metal-organic framework [Cu 2 (EDB) 2 (BPY)] as an efficient and recyclable heterogeneous catalyst (EDB = 4,4'-ethynyldibenzoic acid, BPY = 4,4'-bipyridine). [36,[42][43][44][45][46][47][48][49] Herein, we present the direct oxidative amidation of N,N-dimethylanilines with anhydrides using the metal-organic framework [Cu 2 (EDB) 2 (BPY)] as an efficient and recyclable heterogeneous catalyst (EDB = 4,4'-ethynyldibenzoic acid, BPY = 4,4'-bipyridine).…”

“…[34][35][36][37][38][39][40][41] Among numerous popular MOFs as catalysts, several copper-based structures offer high activity for various organic reactions because of their unsaturated open copper metal sites. [36,[42][43][44][45][46][47][48][49] Herein, we present the direct oxidative amidation of N,N-dimethylanilines with anhydrides using the metal-organic framework [Cu 2 (EDB) 2 (BPY)] as an efficient and recyclable heterogeneous catalyst (EDB = 4,4'-ethynyldibenzoic acid, BPY = 4,4'-bipyridine). To the best of our knowledge, the direct oxidative amidation between tertiary amines and anhydrides as acylation reagents using heterogeneous catalyst is not previously reported.…”

Application of Palladium Encapsulated MOF in Coupling Reaction

“…In recent years, the employment of MOFs as the supports for Pd NPs has attracted considerable interest [24][25][26]. For catalytic applications, Pd NPs have been successfully deposited at the outer surface of the MOF supports (Pd/MOFs) [27][28][29][30][31][32] or loaded inside the cavities of the MOFs (Pd@MOFs) [35][36][37][38][39][40][41] via various methods such as impregnation [27][28][29][30][31][32][33][34][35][36][37][38][39] and chemical vapor deposition [40]. then the catalyst was separated by centrifugation and dried at room temperature.…”

Solvent-free and melt aerobic oxidation of benzyl alcohols using Pd/Cu2(BDC)2DABCO–MOF prepared by one-step and through reduction by dimethylformamide

“…[30][31][32] For catalytic applications, PdNPs have been successfully deposited at the outer surface of the MOF supports (Pd/MOFs) [33][34][35][36][37][38] or loaded inside the cavities of the MOFs (Pd@MOFs) via various methods such as impregnation and chemical vapor deposition. [39][40][41][42][43] Although great efforts have been made in this eld, a general and facile method is needed that can easily introduce the palladium(0) precursor inside the cavities of MOFs in onepot and without any reducing agent and control the formation of PdNPs with a small particle size, which is benecial in the cases such as catalysis. Herein, we report the one-step and reducing-agent-free encapsulation of ultrane PdNPs in to nanopores Cu 2 (BDC) 2 (DABCO) without Pd(0) NPs aggregation on the external surface of framework and application of this catalyst in aerobic oxidation of benzyl alcohols.…”