Well‐Defined NHC−Ni Complexes as Catalysts: Preparation, Structures and Mechanistic Studies in Cross‐Coupling Reactions

Developmental studies are ongoing to discover a way to utilise new N‐heterocyclic carbene (NHC)−Ni complexes as catalysts. Using a bulky NHC ligand, it is possible to synthesise an NHC/phosphine‐mixed heteroleptic Ni(II) complex, which can serve as an excellent catalyst for various cross‐coupling reactions. During the study of the reaction mechanisms using these Ni complexes, NHC−Ni(I) complexes were accidentally discovered, and it was observed that they exhibit excellent catalytic activity for cross‐coupling reactions. The possibility of the presence of NHC−Ni(I) intermediates in these catalytic reaction pathways has been experimentally demonstrated. Depending on the type of reaction, dinuclear Ni(I) and mononuclear Ni(I) complexes can function as intermediates. The results of the investigation of each reaction mechanism are summarised, and the prospects are described.

[1]  S. Ogoshi.  Nickel Catalysis in Organic Synthesis: Methods and Reactions , 2019, Focus on Catalysts.

[2]  G. C. Fu,et al.  Mechanistic Investigation of Enantioconvergent Kumada Reactions of Racemic α-Bromoketones Catalyzed by a Nickel/Bis(oxazoline) Complex. , 2019, Journal of the American Chemical Society.

[3]  T. Fujii,et al.  Fluorine-Substituted Arylphosphine for an NHC-Ni(I) System, Air-Stable in a Solid State but Catalytically Active in Solution , 2019, Molecules.

[4]  D. Yaron,et al.  Photostable Helical Polyfurans. , 2019, Journal of the American Chemical Society.

[5]  R. Thauer.  Methyl (Alkyl)-Coenzyme M Reductases: Nickel F-430-Containing Enzymes Involved in Anaerobic Methane Formation and in Anaerobic Oxidation of Methane or of Short Chain Alkanes , 2019, Biochemistry.

[6]  G. Brudvig,et al.  Development of an Improved System for the Carboxylation of Aryl Halides through Mechanistic Studies. , 2019, ACS catalysis.

[7]  P. Braunstein,et al.  N-Heterocyclic Carbene Complexes of Copper, Nickel, and Cobalt. , 2019, Chemical reviews.

[8]  N. Lehnert,et al.  A Biochemical Nickel(I) State Supports Nucleophilic Alkyl Addition: A Roadmap for Methyl Reactivity in Acetyl Coenzyme A Synthase , 2019, Inorganic chemistry.

[9]  R. Poli,et al.  Homolytically weak metal-carbon bonds make robust controlled radical polymerizations systems for “less-activated monomers” , 2019, Journal of Organometallic Chemistry.

[10]  Peter Chen,et al.  Origin of the Immiscibility of Alkanes and Perfluoroalkanes. , 2019, Journal of the American Chemical Society.

[11]  T. Müller,et al.  3d Transition Metals for C-H Activation. , 2018, Chemical reviews.

[12]  R. Vanderlinden,et al.  Synthesis and Characterization of [(NHC)Ni(styrene)2] Complexes: Isolation of Monocarbene Nickel Complexes and Benchmarking of %VBur in (NHC)Ni-π Systems , 2018, Organometallics.

[13]  W. N. Palmer,et al.  Site-Selective Nickel-Catalyzed Hydrogen Isotope Exchange in N-Heterocycles and Its Application to the Tritiation of Pharmaceuticals , 2018, ACS Catalysis.

[14]  Lillian V. A. Hale,et al.  Intermediacy of Ni-Ni Species in sp2 C-O Bond Cleavage of Aryl Esters: Relevance in Catalytic C-Si Bond Formation. , 2018, Journal of the American Chemical Society.

[15]  Michael T Robo,et al.  Stable, Well-Defined Nickel(0) Catalysts for Catalytic C-C and C-N Bond Formation. , 2018, ACS catalysis.

[16]  K. Okuma,et al.  Buchwald-Hartwig Amination of Phosphinines and the Effect of Amine Substituents on Optoelectronic Properties of the Resulting Coupling Products. , 2018, The Journal of organic chemistry.

[17]  B. Liu,et al.  C-N Cross-Coupling via Photoexcitation of Nickel-Amine Complexes. , 2018, Journal of the American Chemical Society.

[18]  P. Kennepohl,et al.  Disproportionation Reactions of an Organometallic Ni(I) Amidate Complex: Scope and Mechanistic Investigations , 2018 .

[19]  G. Brudvig,et al.  Nickel(I) Aryl Species: Synthesis, Properties, and Catalytic Activity. , 2018, ACS catalysis.

[20]  Yuji Koga,et al.  Dinuclear Nickel(I) and Palladium(I) Complexes for Highly Active Transformations of Organic Compounds , 2018, Molecules.

[21]  Eduardo Peris,et al.  Smart N-Heterocyclic Carbene Ligands in Catalysis. , 2017, Chemical reviews.

[22]  F. Maseras,et al.  Oxidative Coupling Mechanisms: Current State of Understanding , 2017 .

[23]  J. Hartwig,et al.  Mechanistic Investigations of the Hydrogenolysis of Diaryl Ethers Catalyzed by Nickel Complexes of N-Heterocyclic Carbene Ligands. , 2017, Journal of the American Chemical Society.

[24]  Ulf‐Peter Apfel,et al.  Mechanistic Implications for the Ni(I)-Catalyzed Kumada Cross-Coupling Reaction , 2017 .

[25]  M. Zeller,et al.  Catalytic Carbonylative Rearrangement of Norbornadiene via Dinuclear Carbon-Carbon Oxidative Addition. , 2017, Journal of the American Chemical Society.

[26]  Indrek Kalvet,et al.  Divergent Reactivity of a Dinuclear (NHC)Nickel(I) Catalyst versus Nickel(0) Enables Chemoselective Trifluoromethylselenolation , 2017, Angewandte Chemie.

[27]  P. Budzelaar,et al.  Catalysis of Cross-Coupling and Homocoupling Reactions of Aryl Halides Utilizing Ni(0), Ni(I), and Ni(II) Precursors; Ni(0) Compounds as the Probable Catalytic Species but Ni(I) Compounds as Intermediates and Products , 2017 .

[28]  Indrek Kalvet,et al.  Striking Divergence in Reactivity of a Dinuclear (NHC)Ni(I) Catalyst vs Ni(0) enables Chemoselective Trifluoromethylselenolation , 2017 .

[29]  Samuel A. Johnson,et al.  Nickel-Catalyzed C-H Silylation of Arenes with Vinylsilanes: Rapid and Reversible β-Si Elimination. , 2017, Journal of the American Chemical Society.

[30]  A. Kaga,et al.  Engaging Radicals in Transition Metal-Catalyzed Cross-Coupling with Alkyl Electrophiles: Recent Advances , 2017 .

[31]  G. C. Fu.  Transition-Metal Catalysis of Nucleophilic Substitution Reactions: A Radical Alternative to SN1 and SN2 Processes , 2017, ACS central science.

[32]  D. J. Nelson,et al.  Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex: mechanism and structure/reactivity relationships , 2017 .

[33]  C. Limberg,et al.  Activation of Small Molecules at Nickel(I) Moieties. , 2017, Journal of the American Chemical Society.

[34]  Q. Guo,et al.  When Weaker Can Be Tougher: The Role of Oxidation State (I) in P- vs N-Ligand-Derived Ni-Catalyzed Trifluoromethylthiolation of Aryl Halides , 2017, ACS catalysis.

[35]  L. Veiros,et al.  Dinuclear Systems in the Efficient Nickel-Catalyzed Kumada–Tamao–Corriu Cross-Coupling of Aryl Halides , 2017 .

[36]  H. Yorimitsu,et al.  Nickel-Catalyzed Boron Insertion into the C2-O Bond of Benzofurans. , 2016, Journal of the American Chemical Society.

[37]  Shinji Kanegawa,et al.  Monomeric Three-Coordinate N-Heterocyclic Carbene Nickel(I) Complexes: Synthesis, Structures, and Catalytic Applications in Cross-Coupling Reactions , 2016 .

[38]  Amanda R. Corcos,et al.  Synthesis, structures, and catalytic reactivity of bis(N-heterocyclic carbene) supported diphenyldiazomethane and 1-azidoadamantane complexes of nickel , 2016 .

[39]  R. Gil,et al.  Nickel-Catalyzed Suzuki Polycondensation for Controlled Synthesis of Ester-Functionalized Conjugated Polymers , 2016 .

[40]  Jie Zhang,et al.  Nickel-Catalyzed Reductive Cross-Coupling of Benzyl Chlorides with Aryl Chlorides/Fluorides: A One-Pot Synthesis of Diarylmethanes. , 2016, Organic letters.

[41]  B. Feringa,et al.  Nickel-Catalyzed Cross-Coupling of Organolithium Reagents with (Hetero)Aryl Electrophiles. , 2016, Chemistry.

[42]  C. Uyeda,et al.  Catalytically Active Nickel–Nickel Bonds Using Redox-Active Ligands , 2016 .

[43]  Mickaël Henrion,et al.  Nickel N-Heterocyclic Carbene-Catalyzed C–Heteroatom Bond Formation, Reduction, and Oxidation: Reactions and Mechanistic Aspects , 2016 .

[44]  Jie Zhang,et al.  Mixed NHC/Phosphine Ni(II) Complexes: Synthesis and Their Applications as Versatile Catalysts for Selective Cross-Couplings of ArMgX with Aryl Chlorides, Fluorides, and Methyl Ethers , 2015 .

[45]  Wen‐Hua Sun,et al.  NMR and EPR Spectroscopic Identification of Intermediates Formed upon Activation of 8-Mesitylimino-5,6,7-trihydroquinolylnickel Dichloride with AlR2Cl (R = Me, Et) , 2015 .

[46]  N. Chatani,et al.  Cross-Couplings Using Aryl Ethers via C-O Bond Activation Enabled by Nickel Catalysts. , 2015, Accounts of chemical research.

[47]  P. Ghosh,et al.  Nickel N-heterocyclic carbene complexes and their utility in homogeneous catalysis , 2015 .

[48]  T. Hasegawa.  Understanding of the intrinsic difference between normal- and perfluoro-alkyl compounds toward total understanding of material properties , 2015 .

[49]  Indrek Kalvet,et al.  Fundamental studies and development of nickel-catalyzed trifluoromethylthiolation of aryl chlorides: active catalytic species and key roles of ligand and traceless MeCN additive revealed. , 2015, Journal of the American Chemical Society.

[50]  Zhangjie Shi,et al.  Exploration of earth-abundant transition metals (Fe, Co, and Ni) as catalysts in unreactive chemical bond activations. , 2015, Accounts of chemical research.

[51]  H. Takaya,et al.  Investigation of Organoiron Catalysis in Kumada–Tamao–Corriu-Type Cross-Coupling Reaction Assisted by Solution-Phase X-ray Absorption Spectroscopy , 2015 .

[52]  I. Pápai,et al.  Superstable Palladium(0) Complex as an Air- and Thermostable Catalyst for Suzuki Coupling Reactions , 2015 .

[53]  G. C. Fu,et al.  Nickel-Catalyzed Negishi Arylations of Propargylic Bromides: A Mechanistic Investigation , 2014, Journal of the American Chemical Society.

[54]  T. Tilley,et al.  Useful Method for the Preparation of Low-Coordinate Nickel(I) Complexes via Transformations of the Ni(I) Bis(amido) Complex K{Ni[N(SiMe3)(2,6-iPr2-C6H3)]2} , 2014, Organometallics.

[55]  A. Osuka,et al.  Practical, modular, and general synthesis of benzofurans through extended Pummerer annulation/cross-coupling strategy. , 2014, Angewandte Chemie.

[56]  F. Glorius,et al.  An overview of N-heterocyclic carbenes , 2014, Nature.

[57]  A. Slawin,et al.  Nickel-catalysed carboxylation of organoboronates. , 2014, Chemical communications.

[58]  D. J. Nelson,et al.  Efficient C-N and C-S bond formation using the highly active [Ni(allyl)Cl(IPr*OMe)] precatalyst , 2014 .

[59]  T. Jamison,et al.  Recent advances in homogeneous nickel catalysis , 2014, Nature.

[60]  M. Ohashi,et al.  One-Pot, Single-Step, and Gram-Scale Synthesis of Mononuclear [(η6-arene)Ni(N-heterocyclic carbene)] Complexes: Useful Precursors of the Ni0–NHC Unit , 2014 .

[61]  A. Slawin,et al.  Enhanced activity of [Ni(NHC)CpCl] complexes in arylamination catalysis , 2013 .

[62]  A. Mori,et al.  Murahashi coupling polymerization: nickel(II)-N-heterocyclic carbene complex-catalyzed polycondensation of organolithium species of (hetero)arenes. , 2013, Journal of the American Chemical Society.

[63]  A. Slawin,et al.  Steric and Electronic Parameters of a Bulky yet Flexible N-Heterocyclic Carbene: 1,3-Bis(2,6-bis(1-ethylpropyl)phenyl)imidazol-2-ylidene (IPent) , 2013 .

[64]  Fu‐She Han.  Transition-metal-catalyzed Suzuki-Miyaura cross-coupling reactions: a remarkable advance from palladium to nickel catalysts. , 2013, Chemical Society reviews.

[65]  T. H. Warren,et al.  β-Diketiminato Nickel Imides in Catalytic Nitrene Transfer to Isocyanides , 2013 .

[66]  Andrés G. Algarra,et al.  Three-coordinate nickel(I) complexes stabilised by six-, seven- and eight-membered ring n-heterocyclic carbenes: synthesis, EPR/DFT studies and catalytic activity. , 2013, Chemistry.

[67]  Shota Tanaka,et al.  Concise synthesis of well-defined linear and branched oligothiophenes with nickel-catalyzed regiocontrolled cross-coupling of 3-substituted thiophenes by catalytically generated magnesium amide. , 2013, Chemistry.

[68]  E. Álvarez,et al.  Synthesis, Structural Characterization, and Catalytic Activity of IPrNi(styrene)2 in the Amination of Aryl Tosylates , 2012 .

[69]  N. Hazari,et al.  Stoichiometric and Catalytic Reactions of Thermally Stable Nickel(0) NHC Complexes , 2012 .

[70]  Yuji Koga,et al.  Monovalent Nickel Complex Bearing a Bulky N-Heterocyclic Carbene Catalyzes Buchwald–Hartwig Amination of Aryl Halides under Mild Conditions , 2011 .

[71]  Xile Hu.  Nickel-catalyzed cross coupling of non-activated alkyl halides: a mechanistic perspective , 2011 .

[72]  Samuel A. Johnson,et al.  Mechanistic implications of an asymmetric intermediate in catalytic C-C coupling by a dinuclear nickel complex. , 2011, Chemical communications.

[73]  A. Mori,et al.  C-H functionalization polycondensation of chlorothiophenes in the presence of nickel catalyst with stoichiometric or catalytically generated magnesium amide. , 2011, Journal of the American Chemical Society.

[74]  M. Conda-Sheridan,et al.  N-Heterocyclic Carbene Bound Nickel(I) Complexes and Their Roles in Catalysis. , 2011, Organometallics.

[75]  M. Page,et al.  Ni(I) and Ni(II) ring-expanded N-heterocyclic carbene complexes: C-H activation, indole elimination and catalytic hydrodehalogenation. , 2010, Chemical communications.

[76]  D. Vicic,et al.  Rapid and selective catalytic oxidation of secondary alcohols at room temperature by using (N-heterocyclic carbene)-ni(0) systems. , 2010, Chemistry.

[77]  Yuji Koga,et al.  A new aspect of nickel-catalyzed Grignard cross-coupling reactions: selective synthesis, structure, and catalytic behavior of a T-shape three-coordinate nickel(I) chloride bearing a bulky NHC ligand. , 2010, Chemical communications.

[78]  D. Cárdenas,et al.  Nickel-catalyzed cross-coupling of alkyl zinc halides for the formation of C(sp(2))-C(sp(3)) bonds: scope and mechanism. , 2009, Chemistry.

[79]  Ullrich Jahn,et al.  Radikale und Übergangsmetallkatalyse – eine Allianz par excellence zur Steigerung von Reaktivität und Selektivität in der organischen Chemie , 2009 .

[80]  U. Jahn,et al.  Radicals and transition-metal catalysis: an alliance par excellence to increase reactivity and selectivity in organic chemistry. , 2009, Angewandte Chemie.

[81]  Yuji Koga,et al.  An Unsaturated Nickel(0) NHC Catalyst: Facile Preparation and Structure of Ni(0)(NHC)2, Featuring a Reduction Process from Ni(II)(NHC)(acac)2 , 2008 .

[82]  D. Phillips,et al.  Density functional theory studies of negishi alkyl-alkyl cross-coupling reactions catalyzed by a methylterpyridyl-Ni(I) complex. , 2008, The Journal of organic chemistry.

[83]  D. Laitar,et al.  Generation of a doubly bridging CO2 ligand and deoxygenation of CO2 by an (NHC)Ni(0) complex. , 2007, Journal of the American Chemical Society.

[84]  K. Hara,et al.  Nickel-NHC-catalyzed alpha-arylation of acyclic ketones and amination of haloarenes and unexpected preferential N-arylation of 4-aminopropiophenone. , 2007, The Journal of organic chemistry.

[85]  C. G. Riordan,et al.  Dioxygen activation at monovalent nickel. , 2007, Accounts of chemical research.

[86]  P. Pulay,et al.  Ligand redox effects in the synthesis, electronic structure, and reactivity of an alkyl-alkyl cross-coupling catalyst. , 2006, Journal of the American Chemical Society.

[87]  M. Sigman,et al.  Steric effects in the aerobic oxidation of pi-allylnickel(II) complexes with N-heterocyclic carbenes. , 2006, Inorganic chemistry.

[88]  Kouki Matsubara,et al.  Polycondensation of haloarylketones catalyzed by palladium compounds bearing N-heterocyclic carbene (NHC) ligands , 2006 .

[89]  Kouki Matsubara,et al.  Synthesis and Structures of Nickel Halide Complexes Bearing Mono- and Bis-coordinated N-Heterocyclic Carbene Ligands, Catalyzing Grignard Cross-Coupling Reactions , 2006 .

[90]  G. Jin,et al.  Synthesis, molecular structure and norbornene polymerization behavior of three-coordinate nickel(I) complexes with chelating anilido-imine ligands. , 2006, Dalton transactions.

[91]  A. Chan,et al.  Nickel-catalyzed asymmetric α-arylation of ketone enolates , 2006 .

[92]  R. Schneider,et al.  Nickel(0)/N-heterocyclic carbene complexes catalysed arylation of aromatic diamines , 2005 .

[93]  S. Nolan,et al.  Simple Synthesis of CpNi(NHC)Cl Complexes (Cp = Cyclopentadienyl; NHC = N-Heterocyclic Carbene) , 2005 .

[94]  A. Arif,et al.  Oxygen-induced ligand dehydrogenation of a planar bis-mu-chloronickel(I) dimer featuring an NHC ligand. , 2005, Inorganic chemistry.

[95]  T. J. Anderson,et al.  Evidence for a NiI active species in the catalytic cross-coupling of alkyl electrophiles. , 2004, Journal of the American Chemical Society.

[96]  M. Sigman,et al.  Unusual reactivity of molecular oxygen with pi-allylnickel(N-heterocyclic carbene) chloride complexes. , 2003, Journal of the American Chemical Society.

[97]  W. M. Davis,et al.  Preparation, crystal structure analysis, and catalytic application of [(S)-BINAP]Ni(COD) and [(S)-BINAP]NiBr2 , 2002 .

[98]  S. Buchwald,et al.  Nickel-BINAP Catalyzed Enantioselective a-Arylation of a-Substituted ?-Butyrolactones , 2002 .

[99]  R. Grubbs,et al.  Mechanism and activity of ruthenium olefin metathesis catalysts. , 2001, Journal of the American Chemical Society.

[100]  R. Grubbs,et al.  New insights into the mechanism of ruthenium-catalyzed olefin metathesis reactions. , 2001, Journal of the American Chemical Society.

[101]  R. Grubbs,et al.  The development of L2X2Ru=CHR olefin metathesis catalysts: an organometallic success story. , 2001, Accounts of chemical research.

[102]  Richard A. Jones,et al.  Reactions of Transition-Metal Metallocenes with Stable Carbenes , 1999 .

[103]  G. Gerstberger,et al.  Nickel(II) Complexes of N-Heterocyclic Carbenes† , 1997 .

[104]  王力生.  “P、E、R、S、O、N”保健法 , 1996 .

[105]  A. J. Arduengo,et al.  Electronic stabilization of nucleophilic carbenes , 1992 .

[106]  J. Kochi.  The role of electron transfer and charge transfer in organometallic chemistry , 1980 .

[107]  J. Kochi,et al.  Mechanism of oxidative addition. Reaction of nickel(0) complexes with aromatic halides , 1979 .