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• W3022379649 abstract "The formation of C–C bonds via C–H bond activation has great significance in the field of organic synthesis because it provides an ideal route to the production of valuable chemical compounds. The overall reaction reduces the number of synthetic steps and minimizes by-product formation, thus rendering C–H functionalization environmentally benign and economically attractive. Direct C–H functionalization strategies can facilitate and expedite the synthesis of naturally occurring compounds, biologically active compounds, agriculturally important products, pharmaceutical drug molecules, as well as functional materials. Although various transition-metal complexes can be used as catalysts, nickel-catalyzed C–H activation has become a predominant and ubiquitous research area in organic chemistry because nickel is an abundant, inexpensive metal with unique catalytic activity. The activation of ubiquitous C–H bonds has great significance in the field of organic synthesis given that it represents an ideal method for directly producing valuable chemicals from structurally simple compounds. First-row transition metals have recently been recognized as a potential alternative to noble transition metals because of their low cost, unique reactivity profiles, and easy availability. Among these metals, nickel (Ni) catalysts have drawn considerable attention from the scientific community. This review focuses on Ni-catalyzed C–H functionalization reactions of (hetero)arenes, including alkylation, arylation, alkenylation, alkynylation, borylation, and trifluoromethylation by using non-directing group strategies. In addition, mechanistic aspects of Ni-catalyzed C–H functionalization reactions are discussed because this allows possible new insights into catalyst improvement. The activation of ubiquitous C–H bonds has great significance in the field of organic synthesis given that it represents an ideal method for directly producing valuable chemicals from structurally simple compounds. First-row transition metals have recently been recognized as a potential alternative to noble transition metals because of their low cost, unique reactivity profiles, and easy availability. Among these metals, nickel (Ni) catalysts have drawn considerable attention from the scientific community. This review focuses on Ni-catalyzed C–H functionalization reactions of (hetero)arenes, including alkylation, arylation, alkenylation, alkynylation, borylation, and trifluoromethylation by using non-directing group strategies. In addition, mechanistic aspects of Ni-catalyzed C–H functionalization reactions are discussed because this allows possible new insights into catalyst improvement. The C–H bond is the most important structural unit in an organic compound. Direct C–H bond functionalization of organic compounds to form C–C or C–heteroatom bonds by using transition-metal catalysts is one of the most powerful and attractive methods in organic synthesis1Yang L. Huang H. Transition-metal-catalyzed direct addition of unactivated C‒H bonds to polar unsaturated bonds.Chem. Rev. 2015; 115: 3468-3517Crossref PubMed Scopus (449) Google Scholar, 2Castro L.C.M. Chatani N. Nickel catalysts/N,N′-bidentate directing groups: an excellent partnership in directed C-H activation reactions.Chem. Lett. 2015; 44: 410-421Crossref Scopus (0) Google Scholar, 3Gensch T. Hopkinson M.N. Glorius F. Wencel-Delord J. Mild metal-catalyzed C-H activation: examples and concepts.Chem. Soc. Rev. 2016; 45: 2900-2936Crossref PubMed Google Scholar, 4Hummel J.R. Boerth J.A. Ellman J.A. Transition-metal-catalyzed C-H bond addition to carbonyls, imines, and related polarized π bonds.Chem. Rev. 2017; 117: 9163-9227Crossref PubMed Scopus (0) Google Scholar, 5Park Y. Kim Y. 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In the last few decades, late and noble transition-metal catalysts have been extensively used in C–H bond functionalization because of the straightforward approach in organic synthesis.35Yamaguchi J. Yamaguchi A.D. Itami K. C-H Bond functionalization: emerging synthetic tools for natural products and pharmaceuticals.Angew. Chem. Int. Ed. 2012; 51: 8960-9009Crossref PubMed Scopus (1949) Google Scholar, 36Arockiam P.B. Bruneau C. Dixneuf P.H. Ruthenium(II)-catalyzed C-H bond activation and functionalization.Chem. Rev. 2012; 112: 5879-5918Crossref PubMed Scopus (1881) Google Scholar, 37Kuhl N. Hopkinson M.N. Wencel-Delord J. Glorius F. Beyond directing groups: transition-metal-catalyzed C-H activation of simple arenes.Angew. Chem. Int. Ed. 2012; 51: 10236-10254Crossref PubMed Scopus (1261) Google Scholar, 38Zhang M. Zhang Y. Jie X. Zhao H. Li G. Su W. Recent advances in directed C-H functionalizations using monodentate nitrogen-based directing groups.Org. Chem. 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Catal. 2019; 361: 26-38Crossref Scopus (14) Google Scholar Ni-catalyzed C–C bond formation has recently become a subject of great interest, because of the low cost, ready availability, and the uniqueness of such catalysis.43Standley E.A. Tasker S.Z. Jensen K.L. Jamison T.F. Nickel catalysis: synergy between method development and total synthesis.Acc. Chem. Res. 2015; 48: 1503-1514Crossref PubMed Scopus (86) Google Scholar, 44Henrion M. Ritleng V. Chetcuti M.J. Nickel N-heterocyclic carbene-catalyzed C–C bond formation: reactions and mechanistic aspects.ACS Catal. 2015; 5: 1283-1302Crossref Scopus (87) Google Scholar, 45Prakasham A.P. Ghosh P. Nickel N-heterocyclic carbene complexes and their utility in homogeneous catalysis.Inorg. Chim. Acta. 2015; 431: 61-100Crossref Scopus (83) Google Scholar, 46Ananikov V.P. Nickel: the spirited horseof transition metal catalysis.ACS Catal. 2015; 5: 1964-1971Crossref Scopus (0) Google Scholar Moreover, nickel is capable of existing in various oxidation states, such as Ni(0)−Ni(IV), which provides different redox pathways such as Ni(0)/Ni(II), Ni(I)/Ni(III),47Schley N.D. Fu G.C. Nickel-catalyzed negishi arylations of propargylic bromides: a mechanistic investigation.J. Am. Chem. Soc. 2014; 136: 16588-16593Crossref PubMed Scopus (203) Google Scholar and Ni(0)/Ni(II)/Ni(III)/Ni(I)48Biswas S. Weix D.J. Mechanism and selectivity in nickel-catalyzed cross-electrophile coupling of aryl halides with alkyl halides.J. Am. Chem. Soc. 2013; 135: 16192-16197Crossref PubMed Scopus (283) Google Scholar,49Zuo Z. Ahneman D.T. Chu L. Terrett J.A. Doyle A.G. MacMillan D.W.C. Merging photoredox with nickel catalysis: coupling of α-carboxyl sp3-carbons with aryl halides.Science. 2014; 345: 437-440Crossref PubMed Scopus (741) Google Scholar during reactions. This propensity of nickel enables catalytic reactions that are mechanistically distinct from those for other metals. Various nickel complexes have been extensively used as catalysts in a wide variety of organic transformations, including cross coupling, cycloaddition, carbonylation, decarbonylation, and polymerization, which contributes both to academic endeavors, as well as in industrial processes.50Thakur A. Louie J. Advances in nickel-catalyzed cycloaddition reactions to construct carbocycles and heterocycles.Acc. Chem. Res. 2015; 48: 2354-2365Crossref PubMed Scopus (45) Google Scholar, 51John A. Miranda M.O. Ding K. Dereli B. Ortuño M.A. LaPointe A.M. Coates G.W. Cramer C.J. Tolman W.B. Nickel catalysts for the dehydrative decarbonylation of carboxylic acids to alkenes.Organometallics. 2016; 35: 2391-2400Crossref Scopus (23) Google Scholar, 52Jacobsen E.N. Breinbauer R. 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Chem. Soc. 1963; 85: 1544-1545Crossref Scopus (211) Google Scholar who observed that heating dicyclopentadienylnickel with diazobenzene afforded a purple-blue colored organo-nickel species. Nevertheless, compared with other transition metals, Ni-catalyzed C–H bond activation has remained relatively undeveloped. Numerous attempts have been made to isolate Ni–H species by the oxidative addition of a C–H bond by Ni(0) complexes. However, only η2-arene compexes were formed and the expected Ni–H complexes could be isolated only when polyfluoroarenes were used.62Kanyiva K.S. Kashihara N. Nakao Y. Hiyama T. Ohashi M. Ogoshi S. Hydrofluoroarylation of alkynes with fluoroarenes.Dalton Trans. 2010; 39: 10483-10494Crossref PubMed Scopus (48) Google Scholar,63Johnson S.A. Huff C.W. Mustafa F. Saliba M. Unexpected intermediates and products in the C-F bond activation of tetrafluorobenzenes with a bis(triethylphosphine)nickel Synthon: direct evidence of a rapid and reversible C-H bond activation by Ni(0).J. Am. Chem. Soc. 2008; 130: 17278-17280Crossref PubMed Scopus (0) Google Scholar Perutz conducted a density functional theory (DFT) study of the oxidative addition of a C–H bond of benzene by a hypothetical (H2PCH2CH2PH2)Ni(0) complex and showed that oxidative addition is kinetically favored, but thermodynamically disfavored because the Ni–C bond strength is significantly lower than that for noble metals, which decreases the thermodynamic driving force for these C–H bond cleavage reactions.64Reinhold M. McGrady J.E. Perutz R.N. A Comparison of C-F and C-H bond activation by zerovalent Ni and Pt: A density functional study.J. Am. Chem. Soc. 2004; 126: 5268-5276Crossref PubMed Scopus (165) Google Scholar However, the presence of a fluorine atom makes the Ni–C bond strong. Because of this, many groups focused on the use of polyfluoroarenes in Ni-catalyzed and promoted reactions.65Clot E. Mégret C. Eisenstein O. Perutz R.N. Exceptional sensitivity of metal-aryl bond energies to Ortho-fluorine substituents: influence of the metal, the coordination sphere, and the spectator ligands on M-C/H-C bond energy correlations.J. Am. Chem. Soc. 2009; 131: 7817-7827Crossref PubMed Scopus (122) Google Scholar,66Doster M.E. Hatnean J.A. Jeftic T. Modi S. Johnson S.A. Catalytic C-H bond stannylation: a new regioselective pathway to C‒Sn bonds via C-H bond functionalization.J. Am. Chem. Soc. 2010; 132: 11923-11925Crossref PubMed Scopus (72) Google Scholar This appears to be related to the fact that most of the Ni-catalyzed C–H functionalization reactions that involve the use of a non-directing-group strategy are limited to acidic C–H bonds. New pathways have, however, been proposed for Ni-catalyzed C–H functionalization reactions, where C–H activation occurs through ligand-to-ligand hydrogen transfer (LLHT) rather than the oxidative addition of a C–H bond,67Guihaumé J. Halbert S. Eisenstein O. Perutz R.N. Hydrofluoroarylation of alkynes with Ni catalysts. C-H activation via ligand-to-ligand hydrogen transfer, an alternative to oxidative addition.Organometallics. 2012; 31: 1300-1314Crossref Scopus (0) Google Scholar which is discussed below (Scheme 20). We recently summarized and discussed recent discoveries in Ni-catalyzed C–H functionalization reactions in which a directing-group strategy is used.68Khake S.M. Chatani N. Chelation-assisted nickel-catalyzed C-H functionalizations.Trends Chem. 2019; 1: 524-539Abstract Full Text Full Text PDF Scopus (0) Google Scholar Although non-directing-group strategies for C–H functionalization have been less explored compared with directing-group strategies because most of the Ni-catalyzed C‒H functionalization reactions by using non-directing-group strategies are limited to an acidic C–H bonds. However, this field has recently made great progress. Herein, we summarize Ni-catalyzed C–H functionalizations in which a non-directing-group strategy is used (See Figure 1). A pioneering example of Ni(0)-catalyzed C–H functionalization was reported by Cavell in 2004, where the coupling of imidazolium salts with alkenes was achieved by using a Ni(cod)2/PPh3 catalyst system (Scheme 1A).69Clement N.D. Cavell K.J. Transition-metal-catalyzed reactions involving imidazolium salt/N-heterocyclic carbene couples as substrates.Angew. Chem. Int. Ed. 2004; 43: 3845-3847Crossref PubMed Scopus (128) Google Scholar Various 1-alkenes, such as 1-hexene, ethylene, and styrene underwent C–H coupling with imidazolium salts. The reaction was proposed to proceed through the oxidative addition of a C–H bond to low-valent Ni(PPh3)n, which is generated in situ, the insertion of an alkene into a H–Ni bond, followed by reductive elimination. In 2008, Hiyama reported the Ni(0)-catalyzed C–H alkylation of pentafluorobenzene with 1-phenyl-1,3-butadiene and 2-vinylnaphthalene (Scheme 1B).70Nakao Y. Kashihara N. Kanyiva K.S. Hiyama T. Nickel-catalyzed alkenylation and alkylation of fluoroarenes via activation of C-H bond over C-F bond.J. Am. Chem. Soc. 2008; 130: 16170-16171Crossref PubMed Scopus (217) Google Scholar The reaction was also proposed to proceed the oxidative addition of a C–H bond to a Ni(0) complex. Applicability of only polyfluoroarenes limits the scope of reaction. The fact that the reaction is only applicable to pentafluorobenzene limits the scope. In a subsequent study, Miura reported on the selective, Ni(0)-catalyzed branched alkylation of 2-phenyl-1,3,4-oxadiazoles with styrene derivatives (Scheme 1C),71Mukai T. Hirano K. Satoh T. Miura M. Nickel-catalyzed C-H alkenylation and alkylation of 1,3,4-oxadiazoles with alkynes and styrenes.J. Org. Chem. 2009; 74: 6410-6413Crossref PubMed Scopus (89) Google Scholar in which the reaction proceeded successfully only when styrenes were used as alkylating reagents, and aliphatic alkenes and acrylic esters were ineffective. In 2010, Hiyama developed a Ni(cod)2/IMes catalytic system for use in the branched selective alkylation of heteroarenes with styrene, in which the reaction was proposed to proceed through the oxidative addition of a C–H bond to Ni(0) followed by the hydroarylation of the alkene (Scheme 1D).72Nakao Y. Kashihara N. Kanyiva K.S. Hiyama T. Nickel-catalyzed hydroheteroarylation of vinylarenes.Angew. Chem. Int. Ed. 2010; 49: 4451-4454Crossref PubMed Scopus (133) Google Scholar This method provides efficient branch-selective alkylation of various heteroarenes. In 2017, Mandal reported a branch-selective C–H alkylation of benzoxazoles with styrenes in the presence of Ni(cod)2 and an abnormal NHC ligand (Scheme 1E).73Vijaykumar G. Jose A. Vardhanapu P.K. P S. Mandal S.K. Abnormal-NHC-supported nickel catalysts for hydroheteroarylation of vinylarenes.Organometallics. 2017; 36: 4753-4758Crossref Scopus (15) Google Scholar In 2010, Hirano and Miura successfully developed the Ni(II)-catalyzed direct alkylation of benzothiazoles with β-hydrogen containing alkyl bromides, although these alkyl bromides are prone to undergoing β-H elimination (Scheme 2A).74Yao T. Hirano K. Satoh T. Miura M. Palladium- and nickel-catalyzed direct alkylation of azoles with unactivated alkyl bromides and chlorides.Chemistry. 2010; 16: 12307-12311Crossref PubMed Scopus (75) Google Scholar In the same year, Hu also reported the alkylation of aromatic heterocycles with alkyl halides in the presence of a (NNN)-pincer Ni(II)complex 1, CuI as a co-catalyst, and LiOtBu as a base (Scheme 2B).75Vechorkin O. Proust V. Hu X. The nickel/copper-catalyzed direct alkylation of heterocyclic C-H bonds.Angew. Chem. Int. Ed. 2010; 49: 3061-3064Crossref PubMed Scopus (147) Google Scholar Ackermann subsequently reported the direct alkylation of benzoxazoles and benzothiazoles with alkyl halides by using a [(diglyme)NiBr2] catalyst, CuI as a co-catalyst, and LiOtBu as a base (Scheme 2C).76Ackermann L. Punji B. Song W. User-friendly [(diglyme)NiBr2]-catalyzed direct alkylations of heteroarenes with unactivated alkyl halides through C–H bond cleavages.Adv. Synth. Catal. 2011; 353: 3325-3329Crossref Scopus (50) Google Scholar The use of 6-bromo-1-hexene as an alkyl halide gave rise to the 5-exo-cyclized product and the use of cyclopropylmethyl bromide gave a ring-opening product, indicating that a radical mechanism is involved. In 2016, Punji reported the use of a (NNN)-pincer Ni(II) complex 2 for the C–H alkylation of azoles without the need for CuI as a co-catalyst (Scheme 2D).77Patel U.N. Pandey D.K. Gonnade R.G. Punji B. Synthesis of quinoline-based NNN-pincer nickel(II) complexes: a robust and improved catalyst system for C–H bond alkylation of azoles with alkyl halides.Organometallics. 2016; 35: 1785-1793Crossref Scopus (20) Google Scholar Qu and Guo developed a new protocol for the direct C–H bond alkylation of N-aromatic heterocycles with alkyl Grignard reagents (Scheme 3A).78Xin P.Y. Niu H.Y. Qu G.R. Ding R.F. Guo H.M. Nickel catalyzed alkylation of N-aromatic heterocycles with Grignard reagents through direct C–H bond functionalization.Chem. Commun. (Camb.). 2012; 48: 6717-6719Crossref PubMed Scopus (40) Google Scholar This reaction provides for the efficient coupling of various alkyl Grignard reagents with N-aromatic heterocycles at room temperature. Later, Hirano and Miura reported the Ni(II)-catalyzed direct alkylation of benzoxazole with N-tosylhydrozoneas a carbene source (Scheme 3B).79Yao T. Hirano K. Satoh T. Miura M. Nickel- and cobalt-catalyzed direct alkylation of azoles with N-tosylhydrazones bearing unactivated alkyl groups.Angew. Chem. Int. Ed. 2012; 51: 775-779Crossref PubMed Scopus (164) Google Scholar This catalysis enabled secondary alkyl groups to be introduced into benzoxazole, which is difficult to achieve by using earlier C–H bond alkylation methodologies. Although CoBr2/phen also showed catalytic activity, the substrate scope was quite different. It was found that a NiBr2 complex was effective only for benzoxazoles, whereas a Co complex catalyzes the reaction of 5-aryloxazoles and benzothiazole. In 2019, Nakao and Hartwig reported a ground breaking reaction, which involved the undirected, Ni(0)-catalyzed linear-selective C–H alkylation of electron-neutral arenes, such as benzene or alkylbenzenes with various unactivated alkenes without the use of a directing system (Scheme 4).80Saper N.I. Ohgi A. Small D.W. Semba K. Nakao Y. Hartwig J.F. Nickel-catalysed anti-Markovnikov hydroarylation of unactivated alkenes with unactivated arenes facilitated by non-covalent interactions.Nat. Chem. 2020; 12: 276-283Crossref PubMed Scopus (1) Google Scholar The reaction with internal alkenes also gave a linear alkylated product. Mechanistic studies suggest that the activation of a C–H bond does not proceed through the oxidative addition of a C‒H bond to Ni(0), instead, a LLHT mechanism (see Scheme 20) and reductive elimination is the rate-determining step. The Ni-catalyzed C–H arylation of azoles with aryl halides was independently reported in 2009 by Itami81Canivet J. Yamaguchi J. Ban I. Itami K. Nickel-catalyzed biaryl coupling of heteroarenes and aryl halides/triflates.Org. Lett. 2009; 11: 1733-1736Crossref PubMed Scopus (247) Google Scholarand Miura.82Hachiya H. Hirano K. Satoh T. Miura M. Nickel-catalyzed direct arylation of azoles with aryl bromides.Org. Lett. 2009; 11: 1737-1740Crossref PubMed Scopus (172) Google Scholar Itami demonstrated the cross coupling of azoles with aryl halides and aryl triflates by using Ni(OAc)2/bipy or Ni(OAc)2/dppf catalysts in the presence of LiOtBu (Scheme 5A).81Canivet J. Yamaguchi J. Ban I. Itami K. Nickel-catalyzed biaryl coupling of heteroarenes and aryl halides/triflates.Org. Lett. 2009; 11: 1733-1736Crossref PubMed Scopus (247) Google Scholar The reaction showed a broad substrate scope for structurally diverse heteroarenes, such as thiazoles, benzothiazoles, oxazoles, benzoxazoles, and benzimidazoles. Similarly, Miura developed the arylation of azoles with aryl bromides by using NiBr2·diglyme and Pen Phen, a Zn powder, and LiOtBu(Scheme 5B).82Hachiya H. Hirano K. Satoh T. Miura M. Nickel-catalyzed direct arylation of azoles with aryl bromides.Org. Lett. 2009; 11: 1737-1740Crossref PubMed Scopus (172) Google Scholar In 2010, Hirano and Miura reported the direct, Ni(II)-catalyzed arylation of azoles with arylboronic acids by using air as an oxidant (Scheme 5C).83Hachiya H. Hirano K. Satoh T. Miura M. Oxidative nickel-air catalysis in C-H arylation: direct cross-coupling of" @default.
• W3022379649 created "2020-05-13" @default.
• W3022379649 creator A5020296322 @default.
• W3022379649 creator A5023225667 @default.
• W3022379649 date "2020-05-01" @default.
• W3022379649 modified "2023-10-17" @default.
• W3022379649 title "Nickel-Catalyzed C−H Functionalization Using A Non-directed Strategy" @default.
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