Room-temperature Suzuki-Miyaura Coupling Research Articles

Precise synthesis of conjugated polymers via a scalable and homogeneous room-temperature Suzuki-Miyaura coupling

Precise synthesis of conjugated polymers via a scalable and homogeneous room-temperature Suzuki-Miyaura coupling

Development of a Scalable Route for a Key Thiadiazole Building Block via Sequential Sandmeyer Bromination and Room-Temperature Suzuki–Miyaura Coupling

To avoid the use and handling of Lawesson’s reagent or other thiation agents in the in-house kilolab, a new scalable route to ethyl 5-(2,4-difluorophenyl)-1,3,4-thiadiazole-2-carboxylate (1) was developed. The key to success was the use of a commercially available amino-thiadiazole building block, which was converted into the desired product via a sequence of Sandmeyer bromination and Suzuki–Miyaura coupling. The different parameters of the Pd-catalyzed coupling have been studied in detail and allowed the reaction to be performed under mild conditions at room temperature and with low catalyst loading. The inconsistencies of the initial scale-up runs with regard to the sluggish conversion of the Suzuki–Miyaura coupling due to Cu contamination were addressed, and the findings were directly implemented in the subsequent batches, which finally led to an improved overall understanding and robustness of the process.

Pd-Co nanoalloys nested on CuO nanosheets for efficient electrocatalytic N2 reduction and room-temperature Suzuki-Miyaura coupling reaction.

Due to their synergistic and tunable effects, bimetallic alloy systems have recently attracted considerable attention as superior catalysts. Herein, Pd-Co bimetallic alloy nanoparticles were uniformly deposited onto CuO nanosheet supports. This nanostructured catalyst was first shown to be an effective catalyst to convert N2 to NH3 in 0.1 M KOH with a yield of 10.04 μg h-1 mg-1cat. and a faradaic efficiency of 2.16%. The catalyst also performed well in the Suzuki-Miyaura coupling reaction at room temperature without an inert atmosphere and any toxic solvents. Thus, the catalyst is consistent with the principles of green chemistry. Due to the synergistic effects, this bimetallic Pd-Co catalyst shows higher catalytic activity than its monometallic counterparts. Moreover, the Pd/Co ratio was tuned to achieve the best catalytic performance. Finally, the Pd-Co/CuO catalyst presented good stability and recyclability. The superior catalytic activity of the bimetallic alloy catalyst make it an alternative material for catalytic applications in the future.

Palladium nanoparticles stabilized by phosphine ligand for aqueous phase room temperature suzuki-Miyaura coupling

Water soluble phosphine ligand triphenylphosphine-3,3′,3″-trisulfonic acid trisodium salt (TPPTS) was used as the stabilizer as well as the activator to the palladium nanoparticles, which showed a high catalytic performance for aqueous phase Suzuki-Miyaura coupling reaction at room temperature.

Highly active palladium catalysts containing a 1,10-phenanthroline analogue N-heterocyclic carbene for room temperature Suzuki-Miyaura coupling reactions of aryl chlorides with arylboronic acids in aqueous media

Two new palladium (II) complexes containing a 1,10-phenanthroline analogue N-heterocyclic carbene (NHC) have been synthesized. The complexes were characterized by 1H and 13C NMR spectroscopy and elemental analysis and their structures were determined by single-crystal X-ray diffraction. The NHC-palladium complexes were employed as catalysts for Suzuki-Miyaura coupling reactions of aryl chlorides with arylboronic acids in aqueous media at room temperature. The cross-coupling reactions were highly efficient with low catalysts loadings.

ChemInform Abstract: Magnetic Nanoparticles Supported Oxime Palladacycle as a Highly Efficient and Separable Catalyst for Room Temperature Suzuki—Miyaura Coupling Reaction in Aqueous Media.

AbstractA novel magnetic nanoparticle‐supported oxime palladacycle catalyst is successfully prepared and characterized.

Magnetic nanoparticles supported oxime palladacycle as a highly efficient and separable catalyst for room temperature Suzuki–Miyaura coupling reaction in aqueous media

Magnetic nanoparticles of Fe3O4 supported oxime palladacycle as a novel catalyst for room temperature Suzuki coupling reaction in aqueous media.

Room-temperature palladium-catalysed Suzuki–Miyaura coupling of arylboric acid with aryl chlorides

The first room-temperature Suzuki–Miyaura coupling of aryl-boronic acid with aryl chlorides catalyzed by a Pd(OAc)2/NiXantphos-based system is communicated.

Room-temperature Suzuki–Miyaura coupling of aryl bromides with phenylboronic acid catalyzed by a palladium complex with an inexpensive nitrogen-containing bis(phosphinite) ligand

A palladium(II) complex with a known inexpensive and very easily synthesized nitrogen-containing bis(phosphinite) ligand has been prepared and characterized by spectroscopic and crystallographic studies. The ligand is bound to the metal in a P,P-bidentate coordination mode with a bite angle of 98.90°. This complex was found to be an efficient catalyst for room-temperature Suzuki–Miyaura coupling of a variety of aryl bromides with phenylboronic acid. At 0.1mol% of palladium in DMF/K3PO4 for 24h, the corresponding biaryls were obtained with 75–92% yields. Activated substrates displayed high yields even within minutes.

NHC–Pd(II)–Im (NHC = N-heterocyclic carbene; Im = 1-methylimidazole) complexes as efficient catalysts for Suzuki-Miyaura coupling reactions of aryl chlorides

A new type of well-defined N-heterocyclic carbene (NHC)-palladium chloride-imidazole complexes derived from IPr HCl or IMes HCl, PdCl 2 and 1-methylimidazole exhibits high catalytic activity in the room-temperature Suzuki-Miyaura coupling reactions of aryl or heteroaryl chlorides. Moreover, the large-scale (20.0 mmol) couplings in the presence of 0.01 mol% catalyst loading can also give the corresponding coupling products in high yields.

Generation of an Aromatic Amide‐Derived Phosphane (Aphos) Library by Self‐Assisted Molecular Editing and Applications of Aphos in Room‐Temperature Suzuki–Miyaura Reactions

Aromatic amide-derived phosphanes (Aphos) are hemilabile P,O-coordinating ligands, which, when combined with a Pd precursor, yield a promising precatalyst system for Suzuki-Miyaura cross-coupling reactions. A focused library of Aphos ligands has been constructed for structural optimization, with the target of improving catalytic efficacy. By using microwave irradiation at accurately regulated temperature, an expeditious and reproducible one-pot synthesis and screening protocol was designed and experimentally validated. The success is based on a unique self-assisted molecular editing (SAME) process in which both the substrate and the product molecules catalyze formation of the product. Thus, starting from a 4-chlorobenzamide-derived Aphos as the substrate, parallel reactions with a selected set of arylboronic acids, in the absence of an added external phosphane ligand to Pd, produced a family of structurally edited Aphos ligands. The resultant reaction mixture containing the new Aphos, the Pd species, and the base could be used for in situ screening of the Aphos efficacy in a reference Suzuki-Miyaura coupling reaction. The structures of all Aphos ligands were characterized by 31P NMR spectroscopy and their catalytic profiles in the reference reaction were evaluated by HPLC analysis. These data allowed the identification of an efficient Aphos ligand, capable of promoting room-temperature Suzuki-Miyaura coupling of unactivated and sterically hindered aryl chlorides with arylboronic acids under mildly basic conditions.

Di- t-butyl(ferrocenylmethyl)phosphine: air-stability, structural characterization, coordination chemistry, and application to palladium-catalyzed cross-coupling reactions

Di- t-butyl(ferrocenylmethyl)phosphine ( 1) has been isolated and structurally characterized. This ligand was found to be reasonably air stable as a solid and it has been shown to possess electron donating ability similar to that of tri- i-propylphosphine. A palladium catalyst bearing this ligand performed room temperature Suzuki–Miyaura coupling reactions with aryl bromides. Modest Heck coupling reactivity with aryl bromides was also observed at 100 °C. Complexation of 1 with Pd 2(dba) 3 led to formation of ( 1) 2Pd 0. Addition of 4-bromoanisole to solutions containing both 1 and Pd 2(dba) 3 led to formation of an oxidative addition product when 1:Pd ratios were ⩽1. With a 2:1 ratio of 1:Pd, monophosphine complex formation and oxidative addition were significantly inhibited.