Ligand-free Suzuki Reaction Research Articles

ChemInform Abstract: Arylation of Pyridine N‐Oxides via a Ligand‐Free Suzuki Reaction in Water.

Abstract We report a practical and highly efficient protocol for the arylation of pyridine N -oxides with arylboronic acid through palladium-catalyzed Suzuki reaction in water. This ligand-free Suzuki reaction is performed in the presence of diisopropylamine and gives 2- or 3-arylated pyridyl N -oxide derivatives in good to excellent yields within 1 h.

Arylation of pyridine N-oxides via a ligand-free Suzuki reaction in water

Abstract We report a practical and highly efficient protocol for the arylation of pyridine N -oxides with arylboronic acid through palladium-catalyzed Suzuki reaction in water. This ligand-free Suzuki reaction is performed in the presence of diisopropylamine and gives 2- or 3-arylated pyridyl N -oxide derivatives in good to excellent yields within 1 h.

High Pressure CO2-Controlled Reactor: Suzuki Reaction in CO2-Based Micelle Stabilized by Nonionic Methylated Branched Hydrocarbon Surfactants

A CO2-based micellar system stabilized by nonionic methylated branched hydrocarbon surfactants was used as a microreactor for the ligand-free Suzuki reaction involving the cross-coupling of iodobenzene and 4-methylbenzeneboronic acid to produce p-methyl biphenyl. In the reaction system, the nonionic surfactant (TMN series) acted both as the reducing agent and as the stabilizer of the palladium nanoparticles that were generated. Transmission electron microscopy images demonstrated that the uniform and nanoscale Pd particles with a sharp size distribution were formed in the CO2-based micelle. The effects of reaction parameters, such as surfactant concentration, CO2 pressure, water content, and base selection, on the microenvironment and conversion in CO2-based microemulsion and emulsion are discussed. In this work, we compared the reactivity in different reactive systems including pure water, atmospheric water–cyclohexane microemulsion, and CO2-based microemulsion. Activity in the CO2-based microemulsion was higher than that obtained with the other two catalytic systems. In these processes, the organic base played a role similar to that of the interface phase-transfer catalyst. These synergistic effects could effectively accelerate the reaction.

Preparation and characterization of nano-CaO based on eggshell waste: Novel and green catalytic approach to highly efficient synthesis of pyrano[4,3-b]pyrans

A general and efficient catalytic system for Pd/C-catalyzed ligand-free aerobic Suzuki cross-coupling reactions was developed. The reaction tolerated a wide range of aryl bromides with a hydrophilic group or a hydrophobic group without any additives in water. Moreover, the catalytic system was successfully extended to the cross-couplings of heteroaryl halides with various arylboronic acids. The Pd/C catalyst could be reuse three times without significant loss of catalytic activity. A highly efficient and recyclable catalytic system for the Pd/C-catalyzed, ligand-free Suzuki reaction was developed; a wide range of aryl bromides were tolerated, and the reaction proceeded without any additives in water.

Pd/C-catalyzed ligand-free and aerobic Suzuki reaction in water

A general and efficient catalytic system for Pd/C-catalyzed ligand-free aerobic Suzuki cross-coupling reactions was developed. The reaction tolerated a wide range of aryl bromides with a hydrophilic group or a hydrophobic group without any additives in water. Moreover, the catalytic system was successfully extended to the cross-couplings of heteroaryl halides with various arylboronic acids. The Pd/C catalyst could be reuse three times without significant loss of catalytic activity. A highly efficient and recyclable catalytic system for the Pd/C-catalyzed, ligand-free Suzuki reaction was developed; a wide range of aryl bromides were tolerated, and the reaction proceeded without any additives in water.

Pd-catalyzed ligand-free Suzuki reaction of β-substituted allylic halides with arylboronic acids in water

The combination of Pd(TFA)2 and KOH could efficiently catalyze the reaction of β-substituted allylic halides with arylboronic acids in water.

Novel triphenylamine-based cyclometalated platinum(II) complexes for efficient luminescent oxygen sensing

Novel triphenylamine-based cyclometalated Pt(II) complexes containing a pyridyl moiety have been synthesized and fully characterized. The cyclometalating ligands were prepared via an efficient palladium-catalyzed ligand-free Suzuki reaction of 4-(diphenylamino)phenylboronic acid with 2-pyridyl bromides under aerobic and aqueous conditions. The photophysical properties of the complexes exhibited that introducing an electron-withdrawing group like trifluoromethyl or cyano group on the 5-position of the pyridine ring affected the LUMO level of the Pt(II) complex significantly, resulting in a marked decrease in energy gap. Moreover, the complex with a cyano group at the 5-position imparts a substantial red-shift up to 56 nm. The O2 sensitivity of the complexes was quantitatively evaluated in a polymer film. The results of the O2-sensing sensitivity of the Pt(II) complexes demonstrated that the complex with a nitrile ligand exhibited the highest sensitivity (KSVapp = 0.102 Torr−1). The triphenylamine-based cyclometalated Pt(II) complexes are potential candidates for efficient luminescent oxygen sensing.

Cover Picture: Oxygen-promoted Palladium-on-Carbon-catalyzed Ligand-free Suzuki Reaction for the Synthesis of Heterobiaryls in Aqueous Media (Asian J. Org. Chem. 6/2013)

Cover Picture: Oxygen-promoted Palladium-on-Carbon-catalyzed Ligand-free Suzuki Reaction for the Synthesis of Heterobiaryls in Aqueous Media (Asian J. Org. Chem. 6/2013)

ChemInform Abstract: A Simple and Efficient Approach for the Palladium‐Catalyzed Ligand‐Free Suzuki Reaction in Water.

ChemInformVolume 44, Issue 12 Isocyclic Compounds ChemInform Abstract: A Simple and Efficient Approach for the Palladium-Catalyzed Ligand-Free Suzuki Reaction in Water. Chun Liu, Chun Liu State Key Lab. Fine Chem., Dalian Univ. Technol., Dalian 116024, Peop. Rep. ChinaSearch for more papers by this authorYixia Zhang, Yixia Zhang State Key Lab. Fine Chem., Dalian Univ. Technol., Dalian 116024, Peop. Rep. ChinaSearch for more papers by this authorNing Liu, Ning Liu State Key Lab. Fine Chem., Dalian Univ. Technol., Dalian 116024, Peop. Rep. ChinaSearch for more papers by this authorJieshan Qiu, Jieshan Qiu State Key Lab. Fine Chem., Dalian Univ. Technol., Dalian 116024, Peop. Rep. ChinaSearch for more papers by this author Chun Liu, Chun Liu State Key Lab. Fine Chem., Dalian Univ. Technol., Dalian 116024, Peop. Rep. ChinaSearch for more papers by this authorYixia Zhang, Yixia Zhang State Key Lab. Fine Chem., Dalian Univ. Technol., Dalian 116024, Peop. Rep. ChinaSearch for more papers by this authorNing Liu, Ning Liu State Key Lab. Fine Chem., Dalian Univ. Technol., Dalian 116024, Peop. Rep. ChinaSearch for more papers by this authorJieshan Qiu, Jieshan Qiu State Key Lab. Fine Chem., Dalian Univ. Technol., Dalian 116024, Peop. Rep. ChinaSearch for more papers by this author First published: 14 March 2013 https://doi.org/10.1002/chin.201312076Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume44, Issue12March 19, 2013 RelatedInformation

Palladium-catalyzed ligand-free and aqueous Suzuki reaction for the construction of (hetero)aryl-substituted triphenylamine derivatives

This paper reports an efficient synthesis of triphenylamine (TPA) derivatives via a palladium-catalyzed Suzuki reaction of (hetero)aryl halides with 4-(diphenylamino)phenylboronic acid (DPBA) in aqueous ethanol under aerobic and ligand-free conditions. Heteroaryl halides, namely pyridyl bromides, quinolyl bromides, pyrimidinyl bromides, 2-chloropyrazine and sulfur-containing heteroaryl bromides, could react smoothly with DPBA, affording good to excellent yields under mild conditions. In addition, aryl bromides were also successfully employed in the cross-couplings with DPBA and furnished the products in high yields at room temperature. The cross-coupling of 4-bromobenzonitrile with DPBA gave the desired product in a quantitative yield within 2 min, resulting in a TOF up to 5820 h−1.

Facile synthesis of mono-, bis- and tris-aryl-substituted aniline derivatives in aqueous DMF

A facile, efficient and general protocol for synthesizing a series of mono-, bisand tris-arylsubstituted aniline derivatives is described via the Pd(OAc)2-catalyzed aerobic and ligand-free Suzuki reaction of mono-, diand tribromoanilines with aryl boronic acids in aqueous N,Ndimethylformamide (DMF). This is the first example to prepare 2,6-bisaryl-4-nitroanilines and 2,6-bisarylanilines via a palladium-catalyzed ligand-free Suzuki reaction.

A highly efficient and aerobic protocol for the synthesis of N-heteroaryl substituted 9-arylcarbazolyl derivatives via a palladium-catalyzed ligand-free Suzuki reaction

A palladium-catalyzed aerobic and ligand-free Suzuki reaction in aqueous ethanol has been developed for the synthesis of N-heteroaryl substituted 9-arylcarbazolyl derivatives. A number of N-heteroaryl halides, namely 2-halogenated pyridines, 2-bromoquinoline, 5-bromopyrimidine and 2-chloropyrazine, were coupled with 4-(9H-carbazol-9-yl)phenylboronic acid (CPBA) or 9-phenyl-9H-carbazol-3-ylboronic acid (PCBA) efficiently to afford good to excellent yields in a short reaction time. Moreover, the catalytic system of Pd(OAc)(2)-EtOH/H(2)O-K(2)CO(3) was successfully extended to the cross-couplings of N-heteroaryl halides with various arylboronic acids. The results demonstrated that the cross-coupling reaction in the present protocol was promoted by oxygen.

A simple and efficient approach for the palladium-catalyzed ligand-free Suzuki reaction in water

A general and efficient protocol is described for the palladium-catalyzed ligand-free and aerobic Suzuki reaction in water in the absence of any additive. The results demonstrate that the base played a crucial role in the high efficiency. The Pd(OAc)2/(i-Pr)2NH/H2O system showed the highest catalytic activity towards the Suzuki reaction of a wide range of aryl halides bearing hydrophilic or hydrophobic groups.

Oxygen-promoted PdCl2-catalyzed ligand-free Suzuki reaction in aqueous media

A simple and efficient protocol has been developed for the PdCl(2)-catalyzed ligand-free and aerobic Suzuki reaction of aryl bromides or nitrogen-based heteroaryl bromides with arylboronic acids in good to excellent yields in aqueous ethanol. A systematic investigation on the effect of different atmospheres on the reactivity of the palladium-catalyzed Suzuki reaction has been carried out, the results show that an aerobic atmosphere demonstrates a positive effect on the reactivity of the Suzuki reaction in an aqueous media and a negative effect in a pure organic solvent, which exhibits that the water plays a crucial role for the function of the atmosphere on the palladium-catalyzed ligand-free Suzuki reaction.

A simple and efficient protocol for a palladium-catalyzed ligand-free Suzuki reaction at room temperature in aqueous DMF

A convenient, effective and mild protocol has been developed for the palladium-catalyzed ligand-free Suzuki reaction of aryl bromides with arylboronic acids in aqueous N,N-dimethylformamide (DMF) in the presence of K2CO3 and a catalytic amount of PdCl2 in air at room temperature. It is noteworthy that the volume ratio of water–DMF and base play important roles in the reaction, and various functional groups are tolerated under the optimized conditions. Furthermore, this protocol could be extended to the cross-couplings of nitrogen-based heteroaryl halides with arylboronic acids in moderate to excellent yields.

An Efficient Protocol for a Pd(OAc)2-Catalyzed Ligand-Free Suzuki Reaction in Toluene

An efficient protocol for a Pd(OAc) 2 -catalyzed ligand-free Suzuki reaction of aryl bromides with arylboronic acids in the presence of K 3 PO 4 ·7H 2 O in toluene under mild and aerobic conditions afforded cross-coupling products in good to excellent yields. Under the optimized reaction conditions (i.e., 0.5 mmol ArBr, 0.75 mmol ArB(OH) 2 , 1 mol% Pd(OAc) 2 , 1.0 mmol K 3 PO 4 ·7H 2 O, 2 ml toluene), the Suzuki reaction between 4-nitrobromobenzene and phenylboronic acid afforded a 99% isolated yield in 5 min at 75 °C and a TOF of up to 1 188 h −1 . ：报道了一种甲苯中醋酸钯催化无配体的 Suzuki 反应体系. 以 K 3 PO 4 ·7H 2 O 为碱, 在该体系中可高效进行芳基溴代物和芳基硼酸的 Suzuki 反应, 且具有反应条件温和、无需惰性气体保护等特点. 在 n (ArBr) = 0.5 mmol, n (ArB(OH) 2 ) = 0.75 mmol, x (Pd(OAc) 2 ) = 1 mol%, n (K 3 PO 4 ·7H 2 O) = 1.0 mmol, v (甲苯) = 2 ml 的优化条件下, 4-溴硝基苯和苯硼酸在 75 °C 反应 5 min, 分离收率即达 99%, TOF 高达 1 188 h $ - $1 . We developed a simple and efficient protocol for a Pd(OAc) 2 -catalyzed aerobic ligand-free Suzuki reaction of aryl bromides with arylboronic acids in the presence of K 3 PO 4 ·7H 2 O in toluene.

Synthesis of novel 3,5-dichloro-2-arylpyridines by palladium acetate-catalyzed ligand-free Suzuki reactions in aqueous media.

A highly efficient palladium acetate-catalyzed ligand-free Suzuki reaction of 2,3,5-trichloropyridine with arylboronic acids in aqueous phase was developed. High yields of 3,5-dichloro-2-arylpyridines, a simple Pd source, absence of ligands, and environmentally benign as well as mild reaction conditions are important features of this method.

A fast and oxygen-promoted protocol for the ligand-free Suzuki reaction of 2-halogenated pyridines in aqueous media

A fast protocol has been developed for the construction of 2-aryl-substituted pyridine derivatives by the oxygen-promoted, ligand-free, Pd(OAc)2-catalyzed Suzuki reaction of 2-halogenated pyridines in aqueous isopropanol.

Synthesis of Biaryls and Polyaryls by Ligand-Free Suzuki Reaction in Aqueous Phase

A highly efficient palladium acetate-catalyzed ligand-free Suzuki reaction in aqueous phase was developed in short reaction times (0.5-1 h) at 35 degrees C in air. The key for such a successful catalytic system was the use of a suitable amount of cosolvents in the aqueous phase. The method could be extended to the consecutive multi-Suzuki coupling, and polyaryls were prepared in a single one-pot step in high selectivity and excellent yield under mild reaction conditions (60 degrees C).