Mechanistic study of a switch in the regioselectivity of hydroheteroarylation of styrene catalyzed by bimetallic Ni-Al through C-H activation.

We previously reported a highly efficient protocol for bimetallic Ni-Al-catalyzed hydroheteroarylation of styrene with benzimidazole based on C-H bond activation. We have now delineated the mechanism of this process, providing a rationale for an observed switch in regioselectivity in the presence of the Lewis acid, AlMe3. The present mechanistic study gives insights for the rational development of catalysts that exhibit required linear/branched selectivity.

[1]  N. Chatani,et al.  Nickel-catalyzed direct arylation of C(sp3)-H bonds in aliphatic amides via bidentate-chelation assistance. , 2014, Journal of the American Chemical Society.

[2]  E. Nakamura,et al.  Synthesis of anthranilic acid derivatives through iron-catalyzed ortho amination of aromatic carboxamides with N-chloroamines. , 2014, Journal of the American Chemical Society.

[3]  F. Song,et al.  N-oxide as a traceless oxidizing directing group: mild rhodium(III)-catalyzed C-H olefination for the synthesis of ortho-alkenylated tertiary anilines. , 2013, Angewandte Chemie.

[4]  N. Chatani,et al.  Catalytic functionalization of C(sp2)-H and C(sp3)-H bonds by using bidentate directing groups. , 2013, Angewandte Chemie.

[5]  Naoto Chatani,et al.  Katalytische Funktionalisierung von C(sp2)-H- und C(sp3)-H-Bindungen unter Verwendung von zweizähnigen dirigierenden Gruppen , 2013 .

[6]  Tiow‐Gan Ong,et al.  Tandem isomerization and C-H activation: regioselective hydroheteroarylation of allylarenes. , 2013, Organic letters.

[7]  Yao Fu,et al.  Mechanistic study on ligand-controlled cobalt-catalyzed regioselectivity-switchable hydroarylation of styrenes. , 2013, Chemistry.

[8]  N. Chatani,et al.  Nickel-catalyzed direct alkylation of C-H bonds in benzamides and acrylamides with functionalized alkyl halides via bidentate-chelation assistance. , 2013, Journal of the American Chemical Society.

[9]  M. Kanai,et al.  Cobalt-catalyzed C4-selective direct alkylation of pyridines. , 2013, Angewandte Chemie.

[10]  N. Yoshikai,et al.  Aldimine-directed branched-selective hydroarylation of styrenes. , 2013, Angewandte Chemie.

[11]  F. Song,et al.  Rhodium or ruthenium-catalyzed oxidative C-H/C-H cross-coupling: direct access to extended π-conjugated systems. , 2013, Angewandte Chemie.

[12]  F. Glorius,et al.  Ohne dirigierende Gruppen: übergangsmetallkatalysierte C-H-Aktivierung einfacher Arene , 2012 .

[13]  F. Glorius,et al.  Beyond directing groups: transition-metal-catalyzed C-H activation of simple arenes. , 2012, Angewandte Chemie.

[14]  C. Bruneau,et al.  Ruthenium(II)-catalyzed C-H bond activation and functionalization. , 2012, Chemical reviews.

[15]  Zhaofeng Wang,et al.  Rhodium(III)-catalyzed C-H activation of arenes using a versatile and removable triazene directing group. , 2012, Angewandte Chemie.

[16]  jin-quan yu,et al.  Pd(II)-catalyzed ortho trifluoromethylation of arenes and insights into the coordination mode of acidic amide directing groups. , 2012, Journal of the American Chemical Society.

[17]  S. Nolan,et al.  N-heterocyclic carbene gold(I) and copper(I) complexes in C-H bond activation. , 2012, Accounts of chemical research.

[18]  Fen Wang,et al.  C-C, C-O and C-N bond formation via rhodium(III)-catalyzed oxidative C-H activation. , 2012, Chemical Society reviews.

[19]  Ming‐Shiuan Yu,et al.  The regioselective switch for amino-NHC mediated C-H activation of benzimidazole via Ni-Al synergistic catalysis. , 2012, Organic letters.

[20]  R. Perutz,et al.  Hydrofluoroarylation of Alkynes with Ni Catalysts. C–H Activation via Ligand-to-Ligand Hydrogen Transfer, an Alternative to Oxidative Addition , 2012 .

[21]  L. Ackermann,et al.  Cationic ruthenium(II) catalysts for oxidative C-H/N-H bond functionalizations of anilines with removable directing group: synthesis of indoles in water. , 2012, Organic letters.

[22]  Zhangjie Shi,et al.  N-Directing group assisted rhodium-catalyzed aryl C-H addition to aryl aldehydes. , 2012, Organic letters.

[23]  Shannon S. Stahl,et al.  Kupferkatalysierte aerobe oxidative C‐H‐Funktionalisierungen: Trends und Erkenntnisse zum Mechanismus , 2011 .

[24]  Alison E Wendlandt,et al.  Copper-catalyzed aerobic oxidative C-H functionalizations: trends and mechanistic insights. , 2011, Angewandte Chemie.

[25]  Yoshiaki Nakao,et al.  Transition-Metal-Catalyzed C—H Functionalization for the Synthesis of Substituted Pyridines , 2011 .

[26]  N. Chatani,et al.  Nickel-catalyzed chelation-assisted transformations involving ortho C-H bond activation: regioselective oxidative cycloaddition of aromatic amides to alkynes. , 2011, Journal of the American Chemical Society.

[27]  D. Leow,et al.  Pd(II)-catalyzed para-selective C-H arylation of monosubstituted arenes. , 2011, Journal of the American Chemical Society.

[28]  P. Knochel,et al.  Lewis‐Säure‐vermittelte benzylische Kreuzkupplungen von Pyridinen mit Arylbromiden , 2011 .

[29]  P. Knochel,et al.  Lewis acid promoted benzylic cross-couplings of pyridines with aryl bromides. , 2011, Angewandte Chemie.

[30]  jin-quan yu,et al.  Ligand-promoted C-3 selective C-H olefination of pyridines with Pd catalysts. , 2011, Journal of the American Chemical Society.

[31]  Phil S. Baran,et al.  Wenn C‐H‐Bindungen sprechen könnten – selektive Oxidationen von C‐H‐Bindungen , 2011 .

[32]  P. Baran,et al.  If C-H bonds could talk: selective C-H bond oxidation. , 2011, Angewandte Chemie.

[33]  Daniel Morton,et al.  Guiding principles for site selective and stereoselective intermolecular C-H functionalization by donor/acceptor rhodium carbenes. , 2011, Chemical Society reviews.

[34]  M. Sanford,et al.  Controlling site selectivity in Pd-catalyzed oxidative cross-coupling reactions. , 2011, Journal of the American Chemical Society.

[35]  Ernesto Rufino-Felipe,et al.  Steric control of conformation in self-assembly metallacalix[4]arenes derived from AlMe3 or GaMe3 with benzimidazolyl ligands. , 2011, Chemical communications.

[36]  Chang-Liang Sun,et al.  Direct C-H transformation via iron catalysis. , 2011, Chemical reviews.

[37]  T. Hiyama,et al.  Dehydrogenative [4 + 2] cycloaddition of formamides with alkynes through double C-H activation. , 2011, Journal of the American Chemical Society.

[38]  N. Yoshikai,et al.  Regioselectivity-switchable hydroarylation of styrenes. , 2011, Journal of the American Chemical Society.

[39]  M. Sanford,et al.  Catalyst Control of Site Selectivity in the PdII/IV-Catalyzed Direct Arylation of Naphthalene , 2011 .

[40]  Robert J. Phipps,et al.  A highly para-selective copper(II)-catalyzed direct arylation of aniline and phenol derivatives. , 2011, Angewandte Chemie.

[41]  F. Glorius,et al.  Palladium-catalyzed intermolecular decarboxylative coupling of 2-phenylbenzoic acids with alkynes via C-H and C-C bond activation. , 2010, Journal of the American Chemical Society.

[42]  T. Hiyama,et al.  Selective C-4 alkylation of pyridine by nickel/Lewis acid catalysis. , 2010, Journal of the American Chemical Society.

[43]  G. Yap,et al.  Bimetallic nickel aluminum mediated para-selective alkenylation of pyridine: direct observation of eta2,eta1-pyridine Ni(0)-Al(III) intermediates prior to C-H bond activation. , 2010, Journal of the American Chemical Society.

[44]  T. Hiyama,et al.  Nickel-catalyzed hydroheteroarylation of vinylarenes. , 2010, Angewandte Chemie.

[45]  G. Maestri,et al.  Catalytic C-C coupling through C-H arylation of arenes or heteroarenes , 2010 .

[46]  Melanie S Sanford,et al.  Palladium-catalyzed ligand-directed C-H functionalization reactions. , 2010, Chemical reviews.

[47]  M. Albrecht.  Cyclometalation using d-block transition metals: fundamental aspects and recent trends. , 2010, Chemical reviews.

[48]  J. Ellman,et al.  Rhodium-catalyzed C-C bond formation via heteroatom-directed C-H bond activation. , 2010, Chemical reviews.

[49]  S. Nolan,et al.  Percent buried volume for phosphine and N-heterocyclic carbene ligands: steric properties in organometallic chemistry. , 2010, Chemical communications.

[50]  jin-quan yu,et al.  Ligand-Enabled Reactivity and Selectivity in a Synthetically Versatile Aryl C–H Olefination , 2010, Science.

[51]  L. Ackermann,et al.  Übergangsmetallkatalysierte direkte Arylierungen von (Hetero)Arenen durch C‐H‐Bindungsbruch , 2009 .

[52]  A. Kapdi,et al.  Transition-metal-catalyzed direct arylation of (hetero)arenes by C-H bond cleavage. , 2009, Angewandte Chemie.

[53]  T. Hiyama,et al.  Direct alkenylation and alkylation of pyridone derivatives by Ni/AlMe(3) catalysis. , 2009, Journal of the American Chemical Society.

[54]  O. Daugulis,et al.  Palladium- and copper-catalyzed arylation of carbon-hydrogen bonds. , 2009, Accounts of chemical research.

[55]  G. McGlacken,et al.  Recent advances in aryl-aryl bond formation by direct arylation. , 2009, Chemical Society reviews.

[56]  G. Yap,et al.  Kinetic and Thermodynamic Study of Syn−Anti Isomerization of Nickel Complexes Bearing Amino-Linked N-Heterocyclic Carbene Ligands: The Effect of the Pendant Arm of the NHC , 2009 .

[57]  T. Hiyama,et al.  Regioselective alkenylation of imidazoles by nickel/Lewis acid catalysis , 2009 .

[58]  X. Chen,et al.  Palladium(II)‐katalysierte C‐H‐Aktivierung/C‐C‐Kreuzkupplung: Vielseitigkeit und Anwendbarkeit , 2009 .

[59]  jin-quan yu,et al.  Palladium(II)-catalyzed C-H activation/C-C cross-coupling reactions: versatility and practicality. , 2009, Angewandte Chemie.

[60]  Vittorio Scarano,et al.  SambVca: A Web Application for the Calculation of the Buried Volume of N‐Heterocyclic Carbene Ligands , 2009 .

[61]  T. Hiyama,et al.  Hydrocarbamoylation of unsaturated bonds by nickel/Lewis-acid catalysis. , 2009, Journal of the American Chemical Society.

[62]  Robert J. Phipps,et al.  A Meta-Selective Copper-Catalyzed C–H Bond Arylation , 2009, Science.

[63]  K. Cavell,et al.  Catalytic Annulation of Heterocycles via a Novel Redox Process Involving the Imidazolium Salt N-Heterocyclic Carbene Couple , 2008 .

[64]  T. Hiyama,et al.  A strategy for C-H activation of pyridines: direct C-2 selective alkenylation of pyridines by nickel/Lewis acid catalysis. , 2008, Journal of the American Chemical Society.

[65]  K. Cavell,et al.  Atom-Efficient Catalytic Coupling of Imidazolium Salts with Ethylene Involving Ni−NHC Complexes as Intermediates: A Combined Experimental and DFT Study , 2007 .

[66]  J. Hartwig,et al.  Lewis acid acceleration of C-N bond-forming reductive elimination from heteroarylpalladium complexes and catalytic amidation of heteroaryl bromides. , 2007, Journal of the American Chemical Society.

[67]  T. Satoh,et al.  Catalytic Direct Arylation of Heteroaromatic Compounds , 2007 .

[68]  Mark E. Scott,et al.  Aryl-aryl bond formation by transition-metal-catalyzed direct arylation. , 2007, Chemical reviews.

[69]  K. Godula,et al.  C-H Bond Functionalization in Complex Organic Synthesis , 2006, Science.

[70]  M. Brown,et al.  Direct palladium-catalyzed C-2 and C-3 arylation of indoles: a mechanistic rationale for regioselectivity. , 2005, Journal of the American Chemical Society.

[71]  K. Cavell,et al.  Transition-metal-catalyzed reactions involving imidazolium salt/N-heterocyclic carbene couples as substrates. , 2004, Angewandte Chemie.

[72]  V. Gevorgyan,et al.  Palladium-catalyzed arylation and heteroarylation of indolizines. , 2004, Organic letters.

[73]  K. Cavell,et al.  Oxidative addition of imidazolium salts to Ni(0) and Pd(0): synthesis and structural characterization of unusually stable metal-hydride complexes. , 2004, Angewandte Chemie.

[74]  S. Nolan,et al.  Lewis Acids Accelerate Reductive Elimination of RCN from P2Pd(R)(CN) , 1999 .

[75]  Masahiro Miura,et al.  Palladium-Catalyzed Arylation of Azole Compounds with Aryl Halides in the Presence of Alkali Metal Carbonates and the Use of Copper Iodide in the Reaction , 1998 .

[76]  G. Pályi,et al.  Alkylcobalt carbonyls. 7. (.eta.1-Benzyl)-, (.eta.3-benzyl)-, and (.eta.1-phenylacetyl)cobalt carbonyls , 1986 .

[77]  G. Pályi,et al.  η1-and η3-Benzylcobalt carbonyls , 1982 .