1111266-89-7Relevant articles and documents
Palladium Complexes of Thio/Seleno-Ether Containing N-Heterocyclic Carbenes: Efficient and Reusable Catalyst for Regioselective C-H Bond Arylation
Bhatt, Ramprasad,Bhuvanesh, Nattamai,Sharma, Kamal Nayan,Joshi, Hemant
, p. 532 - 540 (2020)
The synthesis of the novel S,CNHC type half-pincer ligand precursors (L1 and L2) is described herein by using the atom economy reactions of 1-(2-(phenylthio)ethyl)-1H-imidazole with benzyl bromide and bromodiphenylmethane, respectively. The analogous reaction of 1-(2-(phenylselanyl)ethyl)-1H-imidazole with 2-bromoethyl phenyl sulfide has also resulted in a imidazolium bromide (L3) which is a precursor of novel S,CNHC,Se type pincer ligand. The route of silver-NHC transmetalation was employed to get the palladium complexes [Pd(L1/L2–HBr)Cl2] (C1 and C2) and [Pd(L3–HBr)Cl]BF4 (C3). The imidazolium bromide (L1–L3) and palladium complexes (C1–C3) were characterized by using multinuclear NMR and HR-MS. The structure and bonding in the complexes C1 and C2 were validated by X-ray crystallography. Thermally robust and moisture/air insensitive palladium complexes C1–C3 have been explored in the catalysis of C–H bond arylation of imidazoles. The protocol operates under mild reaction conditions in air with an excellent regioselective C–H bond arylation at C-5 position in imidazoles. All the complexes were found to be efficient (yield up to 97 % in 12 h) in the catalysis; however, the activating pincer ligand framework containing Pd catalyst C3, was found to be utmost effective among the three catalysts. Only 0.5 mol-% catalyst loading is required to achieve admirable yield of the desired cross-coupled products. A wide range of substrates was examined, and the developed protocol was applicable to all derivatives with high functional group tolerance and greater efficiency. More importantly, the catalyst C3 has also been found recyclable up to five cycles with minor decrease in efficiency which is highly desirable feature for the development of economical and sustainable industrial reaction processes. The PPh3 and Hg poisoning tests have established the complete homogeneous nature of the catalysis.
Palladium-Based Catalysts Supported by Unsymmetrical XYC–1 Type Pincer Ligands: C5 Arylation of Imidazoles and Synthesis of Octinoxate Utilizing the Mizoroki–Heck Reaction
Maji, Ankur,Singh, Ovender,Singh, Sain,Mohanty, Aurobinda,Maji, Pradip K.,Ghosh, Kaushik
, p. 1596 - 1611 (2020/04/29)
A series of new unsymmetrical (XYC–1 type) palladacycles (C1–C4) were designed and synthesized with simple anchoring ligands L1–4H (L1H = 2-((2-(4-methoxybenzylidene)-1-phenylhydrazinyl)methyl)pyridine, L2H = N,N-dimethyl-4-((2-phenyl-2-(pyridin-2-ylmethyl)hydrazono)methyl)aniline, L3H = N,N-diethyl-4-((2-phenyl-2-(pyridin-2-ylmethyl)hydrazono)methyl) aniline and L4H = 4-(4-((2-phenyl-2-(pyridin-2-ylmethyl)hydrazono) methyl)phenyl)morpholine H = dissociable proton). Molecular structure of catalysts (C1–C4) were further established by single X-ray crystallographic studies. The catalytic performance of palladacycles (C1–C4) was explored with the direct Csp2–H arylation of imidazoles with aryl halide derivatives. These palladacycles were also applied for investigating of Mizoroki–Heck reactions with aryl halides and acrylate derivatives. During catalytic cycle in situ generated Pd(0) nanoparticles were characterized by XPS, SEM and TEM analysis and possible reaction pathways were proposed. The catalyst was employed as a pre-catalyst for the gram-scale synthesis of octinoxate, which is utilized as a UV-B sunscreen agent.
Developing Bis(imino)acenaphthene-Supported N-Heterocyclic Carbene Palladium Precatalysts for Direct Arylation of Azoles
Hu, Li-Qun,Deng, Rong-Li,Li, Yan-Fen,Zeng, Cui-Jin,Shen, Dong-Sheng,Liu, Feng-Shou
, p. 214 - 226 (2018/02/06)
On the basis of the strategy of developing highly efficient protocol for Pd-catalyzed cross-coupling reactions, a series of bulky bis(imino)acenaphthene (BIAN)-supported Pd-PEPPSI complexes were synthesized, characterized, and applied in direct arylation