Suzuki-Miyaura C-C Coupling Reactions Catalyzed by Supported Pd Nanoparticles for the Preparation of Fluorinated Biphenyl Derivatives

Abstract

Heterogeneous recyclable catalysts in Suzuki-Miyaura C-C coupling reactions are of great interest in green chemistry as reusable alternatives to homogeneous Pd complexes. Considering the interesting properties of fluorinated compounds for the pharmaceutical industry, as precursors of novel materials, and also as components of liquid crystalline media, this present study describes the preparation of different fluorinated biphenyl derivatives by Suzuki-Miyaura coupling reactions catalyzed by a heterogeneous system (G-COOH-Pd-10) based on Pd nanoparticles supported onto COOH-modified graphene. The catalytic activity of the hybrid material G-COOH-Pd-10 has been tested in Suzuki-Miyaura C-C coupling reactions observing excellent versatility and good conversion rates in the reactions of phenylboronic acid, 4-vinylphenylboronic acid, 4-carboxyphenylboronic acid, and 4-fluorophenylboronic acid with 1-bromo-4-fluorobenzene. In addition, the influence of the arylbromide has been studied by carrying out reactions of 4-fluorophenylboronic acid with 1-bromo-2-fluorobenzene, 1-bromo-3-fluorobenzene, 1-bromo-4-fluorobenzene, 2-bromo-5-fluorotoluene, and 2-bromo-4-fluorotoluene. Finally, catalyst recyclability tests show a good degree of reusability of the system based on G-COOH-Pd-10 as the decrease in catalytic activity after five consecutive catalytic cycles in the reaction of 1-bromo-4-fluorobenzene with 4-florophenylboronic acid at 48 hours of reaction is lower than 8% while in the case of reactions at three hours the recyclability of the systems is much lower.

Reducing-agent-free facile preparation of Rh-nanoparticles uniformly anchored on onion-like fullerene for catalytic applications

“…Most of the heterogeneous catalysts developed for Suzuki cross-coupling reactions are Pd-based systems. For example, Erami et al , 67 prepared Pd nanoparticles supported G-COOH catalysts for the Suzuki–Miyaura C–C coupling reactions. They found that the resultant Pd-catalyst is highly active, versatile, stable and reusable.…”

“…65 Particularly, the synthesis of biaryl compounds via Suzuki cross-coupling has become one of the most preferred methods in organic chemistry. [40][41][42][43][44][45][46][47][66][67][68][69][70][71][72] In fact, this reaction is workable with wide range of substrates under mild reaction conditions, and the reaction starting material (boronic acid) is highly sustainable and readily available. Moreover, the catalytic products, biaryl compounds, are vastly useful in the production of various pharmaceuticals, liquid crystals, complex drug molecules, ligands and polymers.…”

One-Pot Synthesized Pd@N-Doped Graphene: An Efficient Catalyst for Suzuki–Miyaura Couplings

“…Particularly, the Suzuki-Miyaura reaction is the most important type of coupling reaction and has been extensively applied in the formation of C-C bonds between an organo-boron compound and an organic (pseudo) halide in the presence of transition metals as catalysts [13,14]. In this regard, Pd has been the most versatile catalyst for the formation of C-C bonds, particularly for Suzuki-Miyaura-type cross-coupling reactions [15,16]. Particularly, due to the high surface area and other exciting surface properties of graphene, Pd-based HRG nanocomposites have attained significant attention as a catalyst in this type of reaction [17].…”

Synthesis of Polyflourinated Biphenyls; Pushing the Boundaries of Suzuki–Miyaura Cross Coupling with Electron-Poor Substrates

“… 60 During the preparation of this article, Carrow and co-workers published a study that used arenediazonium salts and fluorinated boronic acids via a cationic transmetalation pathway in a Suzuki–Miyaura coupling. 61 Very recently Pd-nanoparticals 62 and photocatalysis 63 , 64 have been applied to the synthesis of polyfluorinated biphenyls. Especially the latter is very useful for the introduction of perfluoro phenyl moieties.…”