135-69-3Relevant articles and documents
Invisible Chelating Effect Exhibited between Carbodicarbene and Phosphine through π-π Interaction and Implication in the Cross-Coupling Reaction
Shih, Wei-Chih,Chiang, Yun-Ting,Wang, Qing,Wu, Ming-Chun,Yap, Glenn P. A.,Zhao, Lili,Ong, Tiow-Gan
, p. 4287 - 4297 (2017)
Palladium complexes supported with the mixed ligands carbodicarbene (CDC) and different phosphine ligands (PPh3, PTol3, and PCy3) were prepared, and their molecular structures were characterized. Examination of the structures of 2-PPh3 and 2-PTol3 with cis configuration discloses the existence of an unexpected π-π interaction between one phenyl group of the phosphine and the benzimidazole ring of a CDC. The palladium complex 2-PPh3 is an active Suzuki-Miyaura catalyst with a wide scope of substrates containing various functional groups and steric demands. In contrast to electron-withdrawing aryl bromide, the yield of product for electron-rich substrates was improved by adding a catalytic amount of DMSO under aerobic conditions. The solution NMR and structural analysis has revealed that the intramolecular π-π interaction between CDC and phosphine ligands has a positive influence on the activity of the reaction, which is further supported by quantum chemical calculations.
Suzuki-Miyaura cross-coupling catalyzed by protein-stabilized palladium nanoparticles under aerobic conditions in water: Application to a one-pot chemoenzymatic enantioselective synthesis of chiral biaryl alcohols
Prastaro,Ceci,Chiancone,Boffi,Cirilli,Colone,Fabrizi,Stringaro,Cacchi
, p. 1929 - 1932 (2009)
The preparation of palladium nanoparticles stabilized primarily within the protein cavity of a highly thermostable Dps protein (DNA binding protein from starved cells) and the use of this precatalyst system in Suzuki-Miyaura cross-coupling reactions under
Alcoholic solvent-assisted ligand-free room temperature Suzuki-Miyaura cross-coupling reaction
Sarmah, Gayatri,Mondal, Manoj,Bora, Utpal
, p. 495 - 498 (2015)
We have observed the enhancing effect of alcoholic solvents in palladium-catalysed ligand-free Suzuki-Miyaura reactions. No extra additives or ligands are required for the Suzuki-Miyaura reaction of aryl bromides with arylboronic acids when we carried out the reaction in alcoholic or aqueous alcoholic solvents. Moreover, ethanol or aqueous ethanol is found to be a very good solvent for the Suzuki-Miyaura reaction involving electronically diverse aryl bromides and arylboronic acids under mild and ligand-free conditions with low catalyst loading. It is observed from Hg(0) poisoning tests that the in situ generated palladium(0) species is the actual catalytic species for the reaction.
Palladium stabilized by 3,4-dihydroxypyridine-functionalized magnetic Fe3O4 nanoparticles as a reusable and efficient heterogeneous catalyst for Suzuki reactions
Pirhayati, Mozhgan,Veisi, Hojat,Kakanejadifard, Ali
, p. 27252 - 27259 (2016)
A Pd supported on 3,4-dihydroxypyridine (Py)-functionalized Fe3O4 (Fe3O4/Py/Pd) hybrid material has been synthesized for the first time. Inductively coupled plasma (ICP), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and field emission scanning electron microscopy (FESEM) and Fourier transform infrared (FTIR) studies have been used to characterize the catalyst. The catalyst exhibited very high activity for Suzuki coupling reaction of several aryl halides with phenylboronic acids in aqueous phase at room temperature. The most interesting result of this work is the possibility to perform Suzuki reactions of aryl chlorides in the presence of the prepared catalyst. The yields of the products were in the range from 70% to 98%. In this process, the novel catalyst could be recovered in a facile manner from the reaction mixture by applying an external magnet device, and reused more than eight times without any significant loss in activity.
Palladium nanoparticles embedded in metal-organic framework derived porous carbon: Synthesis and application for efficient Suzuki-Miyaura coupling reactions
Dong, Wenhuan,Zhang, Li,Wang, Chenhuan,Feng, Cheng,Shang, Ningzhao,Gao, Shutao,Wang, Chun
, p. 37118 - 37123 (2016)
A nanoporous carbon (NPC) material was prepared by one-step direct carbonization of a metal-organic framework, MOF-5, without additional carbon precursors. Pd nanoparticles were immobilized on the MOF-5-derived NPC by an impregnation method coupled with subsequent reduction with NaBH4. The prepared catalyst was in-depth characterized by X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy, and N2 adsorption. The catalyst was used to catalyze the Suzuki-Miyaura coupling reactions and exhibited high catalytic efficiency with yields ranging from 90% to 99% under mild conditions. The results demonstrated the great application potential of MOF precursor-based metal nanoparticle composites in catalysis.
Importance of monodentate mono-ligand designs in developing N-stabilized Pd catalysts for efficient ambient temperature C[sbnd]C coupling: Donor strengths and steric features
Eseola, Abiodun Omokehinde,G?rls, Helmar,Plass, Winfried
, (2019)
Unfriendly temperature profiles and costs of carbon coupling catalysis, which pose challenge to both synthetic organic chemists as well as industrial applicability, motivated our design of new monodentate N-donors as support ligands for the purpose of constructing ambient temperature precatalysts that are molecularly close to the hypothetical active forms. Therefore, a series of sterically varied monodentate N-donor imidazoles (1–7) and oxazoles (8–9) have been synthesized and their N-donor strengths, which were estimated as pKas, are systematically varied from 0.9 to 8.5 by substituent variations. Eleven target mono-ligand complexes (1-PdCl2MeCN – 9-PdCl2MeCN, 6-PdCl2PhCN and 7-PdCl2PhCN) and six trans-bis-ligand complexes (12-PdCl2, 22-PdCl2, 32-PdCl2, 62-PdCl2, 12-Pd(OAc)2 and 22-Pd(OAc)2) were isolated and catalytically studied along with PdI2(PPh3)2. Results of coupling reactions, which were conducted both via in situ ‘Pd(II) salt + ligand’ approach and by use of the precatalysts, show that the mono-ligand precatalyst designs (1-PdCl2MeCN – 9-PdCl2MeCN, 6-PdCl2PhCN and 7-PdCl2PhCN) represent a true catalyst improvement initiative among the phosphine-free catalyst community; i.e. yields approaching 100% (TOF ≈ 2000) at 0.2 mol % catalyst loading, 45 °C and within 15 min. On the other hand, the complexes with trans-bis-ligand coordination were inactive at ambient temperatures. Therefore, it was concluded that coordinative saturation, which results from implementing two or more ligand equivalents or use of polydentate ligands on palladium, should be strongly discouraged. Such saturation necessitates the undesirable and avoidable high temperature necessities, long reflux durations and needlessly high catalyst loadings. Correlation between catalyst activity and donor strengths or steric properties were analysed leading to important conclusions. The catalyst design also supported coupling of activated aryl chlorides from 60 °C while Heck coupling activities were observed only at the early minutes of reactions.
New biomaterials for Ni biosorption turned into catalysts for Suzuki-Miyaura cross coupling of aryl iodides in green conditions
Adler, Pauline,Boulanger, Clotilde,Cases, Lucie,Diliberto, Sébastien,Grison, Claude,Pelissier, Franck
, p. 28085 - 28091 (2021/09/15)
In parallel with increasing Ni production and utilisation, Ni pollution in the soil-water continuum has become an alarming and global problem. Solutions for removing Ni from industrial effluents have been widely investigated and biosorption has emerged as an efficient, cost-effective, scalable and sustainable alternative for water treatment. However, the biosorption capacity is limited by the chemical composition of the biomaterial and the Ni-enriched biomaterials are rarely valorised. In this work, the biosorption capacity of three abundant biomaterials with different chemical properties - water hyacinth, coffee grounds and pinecones - was studied before and after functionalization, and reached a maximum biosorption capacity of 51 mg g?1of Ni(ii). A bioinspired functionalization approach was investigated introducing carboxylate moieties and was conducted in green conditions. The Ni-enriched biomaterials were valorised by transformation into catalysts, which were characterised by MP-AES and XRPD. Their characterisation revealed a structure similar to nickel formate, and hence the Eco-Ni(HCOO)2catalysts were tested in Suzuki-Miyaura reactions. Several aryl iodides were successfully cross-coupled to phenylboronic acids using Eco-Ni(HCOO)2without any ligand, a mild and green base in a mixture of green solvents.
Visible light-driven Suzuki-Miyaura reaction by self-supported Pd nanocatalysts in the formation of Stille coupling-based photoactive microporous organic polymers
Ahn, Tae Kyu,Choi, Sung Jae,Jo, Bonghyun,Kim, Hae Jin,Ko, Kyoung Chul,Ko, Yoon-Joo,Lee, Sang Moon,Ryu, Sang Hyun,Seon, Ji Hui,Son, Seung Uk
, p. 5535 - 5543 (2020/09/17)
Stille coupling was applied to synthesize microporous organic polymers (MOPs). Metallic Pd was in situ self-supported during the networking of 1,3,6,8-tetrabromopyrene with 1,4-bis(tributylstannyl)benzene to form Stille coupling-based MOP (St-MOP)?Pd. The size of St-MOP particles and the amount of metallic Pd in St-MOP?Pd depended on the amount of Pd catalyst. As the amount of Pd catalyst increased, the size of St-MOP particles decreased with an increase of metallic Pd, due to the increased St-MOP nuclei in the early growth stage of St-MOP. The St-MOP bearing pyrenes showed absorption and emission of visible light and St-MOP?Pd showed excellent catalytic performance in the visible light-driven Suzuki-Miyaura coupling. The optimal St-MOP?Pd-2 (0.14 mol% Pd) showed a TON of 657 and a TOF of 219 h-1 in the visible light-driven Suzuki-Miyaura coupling of 1-acetyl-4-bromobenzene and phenylboronic acid at 25 °C. The optimal amount of St-MOP and metallic Pd in St-MOP?Pd was critical to achieve excellent catalytic performance. The overall photocatalytic principles of St-MOP?Pd were rationalized by computational simulation. This journal is
