101002-44-2Relevant articles and documents
Phosphine mono- and bis-ylide palladacycles as homogeneous molecular precatalysts: Simple and efficient protocol greatly facilitate Suzuki and Heck coupling reactions
Sabounchei, Seyyed Javad,Ahmadi, Mohsen,Panahimehr, Mohammad,Bagherjeri, Fateme Akhlaghi,Nasri, Zahra
, p. 249 - 259 (2014)
Moisture/air-stable and robust phosphine mono- and bis-ylide palladacycles as catalyst precursors were used in Suzuki and Heck cross-coupling reactions with different aryl halides including electron-rich and electron-deficient substituents. These coupling
Synthesis, X-ray structural and DFT studies of n-membered ring P, C-chelated complexes of Pd(II) and pt(II) derived from unsymmetrical phosphorus ylides and application of pd(II) complexes as catalyst in suzuki reaction
Sabounchei, Seyyed Javad,Sayadi, Mohsen,Bayat, Mehdi,Sedghi, Asiyeh,Gable, Robert W.
, p. 3727 - 3748 (2017)
The phosphonium salts [Ph2P(CH2)nPPh2CH2C(O)C6H4-m-OMe]Br (n = 1 (S1) and n = 2 (S2)) were synthesized in the reaction of bis(diphenylphosphino) methane (dppm) and bis(diphenylphosphino)ethane (dppe) with 2-bromo-3?-methoxy acetophenone, respectively. Further treatment with NEt3 gave the phosphorus ylides Ph2P(CH2)nPPh2C(H)C(O)C6H4-m-OMe (n = 1 (Y1) and n = 2 (Y2)). These ligands were treated with [MCl2(cod)] (M = Pd or Pt; cod = 1,5-cyclooctadiene) to give the P, C-chelated complexes, [MCl2(Ph2P(CH2)nPPh2C(H)C(O)C6H4-m-OMe)] (n = 1, M = Pd (3), Pt (4), and n = 2, M = Pd (5), Pt (6)). These compounds were characterized by elemental analysis, spectroscopic methods, UV–visible, and fluorescence emission spectra. Further, the structures of complexes 3 and 6 were characterized crystallographically. The palladium complexes 3 and 5 proved to be excellent catalysts for the Suzuki reactions of various aryl chlorides. Also, a theoretical study on the structure of complexes 3–6 has been investigated at the BP86/def2-SVP level of theory. The strength and nature of donor?acceptor bonds between the phosphorus ylides (L) and MCl2 fragment in the [LMCl2] (M = Pd, Pt, L = Y1, Y2) were studied by NBO and energy decomposition analysis (EDA), as well as their natural orbitals for chemical valence variation (EDA-NOCV).
Functionalized α-keto stabilized sulfonium ylides as highly active ligand precursors for palladium catalyzed Suzuki-Miyaura cross-couplings
Sabounchei, Seyyed Javad,Hashemi, Ali
, p. 123 - 127 (2014)
Five α-keto stabilized sulfonium ylides as type (Me) 2SCHC(O)C6H4-p-X (X = H, Br, NO2, CH3 and OCH3) {L1-L5} were used as ligand precursors in the Suzuki-Miyaura cross-coupling reaction. The best catalytic performance was obtained by using a sulfonium ylide/Pd ratio of 2:1. The catalytic systems displayed high activities, which increased in the order R = NO2 (L3) 2) 1) 3 (L4) 3 (L5). The coupling reactions proceeded smoothly with 0.05 mol% PdCl2 and 0.1 mol% L5 in DMF at 130 °C between varieties of electronically activated, deactivated and neutral aryl halides and aryl boronic acids within short reaction times and without the need for exclusion of air which gave good to high yields of the corresponding products. All the studied ligands demonstrated very high activity in the Suzuki-Miyaura cross-coupling, which yielded turnover numbers up to 1940. Comparative studies showed that the performance of sulfonium ylide L5 is significantly superior to that of related phosphine-free ligands.
Pallada- and platinacycle complexes of phosphorus ylides; synthesis, X-ray characterization, theoretical and electrochemical studies and application of Pd(II) complexes as catalyst in Suzuki-Miyaura coupling reaction
Sabounchei, Seyyed Javad,Sedghi, Asieh,Hashemi, Ali,Hosseinzadeh, Marjan,Bayat, Mehdi,Gable, Robert W.
, (2017)
The new unsymmetrical phosphonium salts [Ph2PCH2PPh2CH2C(O)C6H4R]Br (R= m-Br (S1) and p-CN (S2)) were synthesized in the reaction of 1,1-bis(diphenylphosphino)methane (dppm) and BrCH2C(O)C6H4R (R= m-Br and p-CN) ketones, respectively. Further treatment with NEt3 gave the α-keto stabilized phosphorus ylides Ph2PCH2PPh2C(H)C(O)C6H4R (R= m-Br (Y1) and p-CN (Y2)). These ligands were reacted with [MCl2(cod)] (M= Pd and Pt; cod= 1,5-cyclooctadiene) to give the pallada- and platinacycle complexes [MCl2(Ph2PCH2PPh2C(H)C(O)C6H4R)] (M= Pd, R= m-Br (3); R= p-CN (4) and M= Pt, R= m-Br (5); R= p-CN (6)). Cyclic voltammetry, elemental analysis, IR and NMR (1H, 13C and 31P) spectroscopic methods were used for characterization of the obtained compounds. Further, the structure of complexes 3 and 4 were characterized crystallographically. Palladacycles 3 and 4 were proved to be excellent catalysts for the Suzuki-Miyaura coupling reactions of various aryl chlorides and arylboronic acids in mixed DMF/H2O media. Also, the bonding situations between two interacted fragments [PtCl2] and Y1 and Y2 ligands in platinacycles 5 and 6 were investigated based on DFT method by using NBO, EDA and ETS-NOCV analysis.
Catalytic reduction of nitroarenes and Suzuki-Miyaura reactions using Pd complex stabilized on the functionalized polymeric support
Ariannezhad, Maryam,Esperi, Melika,Pourmorteza, Narges,Yousefi, Abed
, (2022/02/17)
The significance of aromatic amines as crude substances in diverse applications has attracted extensive consideration in the field of economic procedures for the reduction of nitroarenes. Also, the formation of Carbon–Carbon bond as a dominant step in the structure of complex molecules is an important phenomenon in chemical reactions. Improvements of eco-friendly methodologies for reduction process and Carbon–Carbon bond formation have been noticeable. The present work represents through a capable heterogeneous Pd catalyst, the reduction of nitroarenes to the corresponding amines in the presence of N2H4 as a weak hydrogen donor reagent in the room temperature and solvent-free condition was progressed. In addition, several C–C bond formations through Suzuki-Miyaura reaction using one-pot mixture containing aryl halide, arylboronic acid in the presence of Pd catalyst at refluxed condition proceeded. Furthermore, the reusability of Pd catalyst for both reduction and Suzuki reactions showed five successive runs without any significant loss in its activity.
Ferrocenyl palladacycles derived from unsymmetrical pincer-type ligands: Evidence of Pd(0) nanoparticle generation during the Suzuki-Miyaura reaction and applications in the direct arylation of thiazoles and isoxazoles
Maji, Ankur,Singh, Anshu,Mohanty, Aurobinda,Maji, Pradip K.,Ghosh, Kaushik
supporting information, p. 17083 - 17096 (2019/11/26)
A new family of ferrocenyl-palladacycle complexes Pd(L1)Cl (Pd1) and Pd(L2)Cl (Pd2) were synthesized and characterized by UV-visible, IR, ESI-MS, and NMR spectral studies. The molecular structures of Pd1 and Pd2 were determined by X-ray crystallographic studies. Palladacycle catalyzed Suzuki-Miyaura cross-coupling reactions were investigated utilizing the derivatives of phenylboronic acids and substituted chlorobenzenes. Mechanistic investigation authenticated the generation of Pd(0) nanoparticles during the catalytic cycle and the nanoparticles were characterized by XPS, SEM and TEM analysis. Direct C-H arylation of thiazole and isoxazole derivatives employing these ferrocenyl-palladacycle complexes was examined. The reaction model for the arylation reaction implicating the in situ generation of Pd(0) nanoparticles was proposed.
