Effect on orthometallation of NHC palladium complexes toward the catalytic activity studies in Suzuki coupling reaction.

Herein, we report an approach to improve catalytic activity for cross-coupling reactions. N-Heterocyclic carbene (NHC) palladium complexes bearing a nitrogen-based ligand without orthometallation complexes show remarkable activities in Suzuki coupling reaction than orthometallation. Aryl chlorides examples employed in air and ambient temperature in Suzuki coupling reaction to reach completion within few minutes.

[1]  Beibei Ma,et al.  Pd-PEPPSI Complexes Bearing Bulky [(1,2-Di-(tert-butyl)acenaphthyl] (DtBu-An) on N-Heterocarbene Backbones: Highly Efficient for Suzuki–Miyaura Cross-Coupling under Aerobic Conditions , 2016 .

[2]  Zhuofeng Ke,et al.  Sterically Encumbered Tetraarylimidazolium Carbene Pd-PEPPSI Complexes: Highly Efficient Direct Arylation of Imidazoles with Aryl Bromides under Aerobic Conditions , 2016 .

[3]  Lei Wang,et al.  A new library of arsine, stibine-stabilized N-heterocyclic carbene palladium complexes: synthesis, structures and activities in C-C and C-N coupling reactions. , 2014, Dalton transactions.

[4]  T. Strassner,et al.  Cyclometalated 2-Phenylimidazole Palladium Carbene Complexes in the Catalytic Suzuki–Miyaura Cross-Coupling Reaction , 2014 .

[5]  W. Thiel,et al.  An Efficient Palladium N‐Heterocyclic Carbene Catalyst Allowing the Suzuki–Miyaura Cross‐Coupling of Aryl Chlorides and Arylboronic Acids at Room Temperature in Aqueous Solution , 2014 .

[6]  Yi-Xiang Wang,et al.  N-Heterocyclic Carbene–Palladium(II)–4,5-Dihydrooxazole Complexes: Synthesis and Catalytic Activity toward Amination of Aryl Chlorides , 2014 .

[7]  Jennifer L. Farmer,et al.  Room-temperature amination of deactivated aniline and aryl halide partners with carbonate base using a Pd-PEPPSI-IPentCl-o-picoline catalyst. , 2014, Angewandte Chemie.

[8]  S. Nolan,et al.  [Pd(IPr*OMe)(cin)Cl] (cin = Cinnamyl): A Versatile Catalyst for C–N and C–C Bond Formation , 2014 .

[9]  S. Bräse,et al.  Metal-catalyzed cross-coupling reactions and more , 2014 .

[10]  C. Besnard,et al.  Chiral PEPPSI Complexes: Synthesis, Characterization, and Application in Asymmetric Suzuki–Miyaura Coupling Reactions , 2014 .

[11]  Reiner Sebastian Sprick,et al.  (N-heterocyclic carbene)Pd(triethylamine)Cl2as precatalyst for the synthesis of Poly(triarylamine)s , 2013 .

[12]  Lixiong Shao,et al.  Palladium-catalyzed Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids. , 2013, Organic & biomolecular chemistry.

[13]  A. Slawin,et al.  Mixed phosphine/N-heterocyclic carbene palladium complexes: synthesis, characterization and catalytic use in aqueous Suzuki-Miyaura reactions. , 2013, Dalton transactions.

[14]  Á. Molnár.  Palladium-catalyzed coupling reactions : practical aspects and future developments , 2013 .

[15]  A. Slawin,et al.  [Pd(IPr*OMe)(acac)Cl] : tuning the N-heterocyclic carbene in catalytic C-N bond formation , 2013 .

[16]  Lixiong Shao,et al.  N-heterocyclic carbene-palladium(II)-1-methylimidazole complex catalyzed amination between aryl chlorides and amides. , 2012, The Journal of organic chemistry.

[17]  A. Slawin,et al.  [Pd(IPr*)(cinnamyl)Cl]: an efficient pre-catalyst for the preparation of tetra-ortho-substituted biaryls by Suzuki-Miyaura cross-coupling. , 2012, Chemistry.

[18]  Ming‐Tsz Chen,et al.  C–H Bond Activation of Palladium Complexes That Feature Pendant Benzamidinate Ligands and Their Catalytic Behaviours , 2012 .

[19]  M. Turner,et al.  Inhibited Catalyst Activation in (N-Heterocyclic carbene)PdCl2(diethylamine) Complexes by Intramolecular Hydrogen Bonding , 2011 .

[20]  L. Cavallo,et al.  Room-temperature synthesis of tetra-ortho-substituted biaryls by NHC-catalyzed Suzuki-Miyaura couplings. , 2011, Chemistry.

[21]  P. Kumar,et al.  Direct C5-Arylation Reaction between Imidazoles and Aryl Chlorides Catalyzed by Palladium Complexes with Phosphines and N-Heterocyclic Carbenes , 2011 .

[22]  M. Turner,et al.  (N-heterocyclic carbene)PdCl2(TEA) complexes: Studies on the effect of the "throw-away" ligand in catalytic activity , 2011 .

[23]  J. Ying,et al.  Rational exploration of N-heterocyclic carbene (NHC) palladacycle diversity: a highly active and versatile precatalyst for Suzuki-Miyaura coupling reactions of deactivated aryl and alkyl substrates. , 2010, Chemistry.

[24]  A. Slawin,et al.  Mixed Phosphite/N-Heterocyclic Carbene Complexes: Synthesis, Characterization and Catalytic Studies , 2010 .

[25]  H. Lee,et al.  Palladium Complexes with Carbene and Phosphine Ligands: Synthesis, Structural Characterization, and Direct Arylation Reactions between Aryl Halides and Alkynes , 2010 .

[26]  Ka Hou Hoi,et al.  Pd-PEPPSI-IPent: an active, sterically demanding cross-coupling catalyst and its application in the synthesis of tetra-ortho-substituted biaryls. , 2009, Angewandte Chemie.

[27]  J. Ying,et al.  Practical One-Pot, Three-Component Synthesis of N-Heterocyclic Carbene (NHC) Ligated Palladacycles Derived from N,N-Dimethylbenzylamine , 2009 .

[28]  S. Nolan,et al.  Room-temperature activation of aryl chlorides in Suzuki-Miyaura coupling using a [Pd(micro-Cl)Cl(NHC)]2 complex (NHC = N-heterocyclic carbene). , 2008, Chemical communications.

[29]  Jianguo Mei,et al.  Modified (NHC)Pd(allyl)Cl (NHC = N-heterocyclic carbene) complexes for room-temperature Suzuki-Miyaura and Buchwald-Hartwig reactions. , 2006, Journal of the American Chemical Society.

[30]  J. Tsuji,et al.  Palladium Reagents and Catalysts: New Perspectives for the 21st Century , 2005 .

[31]  S. Nolan,et al.  A general method for the Suzuki-Miyaura cross-coupling of sterically hindered aryl chlorides: synthesis of di- and tri-ortho-substituted biaryls in 2-propanol at room temperature. , 2003, Journal of the American Chemical Society.

[32]  R. Bedford.  Palladacyclic catalysts in C-C and C-heteroatom bond-forming reactions. , 2003, Chemical communications.

[33]  G. C. Fu,et al.  Palladium-catalyzed coupling reactions of aryl chlorides. , 2002, Angewandte Chemie.

[34]  S. Nolan,et al.  Activation and Reactivity of (NHC)Pd(allyl)Cl (NHC = N-Heterocyclic Carbene) Complexes in Cross-Coupling Reactions , 2002 .

[35]  W. Herrmann,et al.  A defined N-heterocyclic carbene complex for the palladium-catalyzed Suzuki cross-coupling of aryl chlorides at ambient temperatures. , 2002, Angewandte Chemie.

[36]  M. Beller,et al.  Palladacycles as Efficient Catalysts for Aryl Coupling Reactions , 1995 .

[37]  Norio Miyaura,et al.  A new stereospecific cross-coupling by the palladium-catalyzed reaction of 1-alkenylboranes with 1-alkenyl or 1-alkynyl halides , 1980 .

[38]  D. Milstein,et al.  A general, selective, and facile method for ketone synthesis from acid chlorides and organotin compounds catalyzed by palladium , 1978 .

[39]  Yutaka Shimizu,et al.  REACTIONS OF ALLYLTIN COMPOUNDS III. ALLYLATION OF AROMATIC HALIDES WITH ALLYLTRIBUTYLTIN IN THE PRESENCE OF TETRAKIS(TRIPHENYLPHOSPHINE)PALLADIUM(O) , 1977 .

[40]  H. A. Dieck,et al.  Palladium catalyzed synthesis of aryl, heterocyclic and vinylic acetylene derivatives , 1975 .

[41]  Y. Tohda,et al.  A convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines , 1975 .