Suzuki-Miyaura coupling reactions are promoted by Pd complexes ligated with C2-symmetric multi-dentate N-heterocyclic carbenes derived in situ from Pd(OAc)2 and imidazolium salts. Good to excellent yields were obtained for aryl bromides as substrates. Turnover numbers of up to 105 could be achieved with 5 × 10?4 mol% of Pd(OAc)2/1 × 10?3 mol% NHC precatalyst in 24 h.
References
[1]
Suzuki, A. Recent advances in the cross-coupling reactions of organoboron derivatives with organic electrophiles, 1995–1998. J. Organomet. Chem. 1999, 576, 147–168, doi:10.1016/S0022-328X(98)01055-9.
[2]
Nicolaou, K.C.; Bulger, P.G.; Sarlah, D. Palladium-catalyzed cross-coupling reactions in total synthesis. Angew. Chem. Int. Ed. 2005, 44, 4442–4489, doi:10.1002/anie.200500368.
[3]
Phan, N.T.S.; Sluys, M.V.D.; Jones, C.W. On the nature of the active species in palladium catalyzed Mizoroki-Heck and Suzuki-Miyaura couplings-homogeneous or heterogeneous catalysis, a critical review. Adv. Synth. Catal. 2006, 348, 609–679, doi:10.1002/adsc.200505473.
[4]
Nicolaou, K.C.; Ramanjulu, J.M.; Natarajan, S.; Br?se, S.; Rübsam, F. A Suzuki coupling-macrolactamization approach to the AB-COD bicyclic system of vancomycin. Chem. Commun. 1997, 1899–1900.
[5]
Baudoin, O.; Cesario, M.; Guénard, D.; Guéritte, F. Application of the palladium-catalyzed borylation/Suzuki coupling (BSC) reaction to the synthesis of biologically active biaryl lactams. J. Org. Chem. 2002, 67, 1199–1207, doi:10.1021/jo0160726.
Miyaura, N.; Suzuki, A. Stereoselective synthesis of arylated (E)-alkenes by the reaction of alk-1-enylboranes with aryl halides in the presence of palladium catalyst. J. Chem. Soc. Chem. Commun. 1979, 866–867, doi:10.1039/c39790000866.
[8]
Miyaura, N.; Yanagi, T.; Suzuki, A. The palladium-catalyzed cross-coupling reaction of phenylboronic acid with haloarenes in the presence of bases. Synth. Commun. 1981, 11, 513–519, doi:10.1080/00397918108063618.
[9]
Miyaura, N.; Suzuki, A. Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem. Rev. 1995, 95, 2457–2483, doi:10.1021/cr00039a007.
[10]
Netherton, M.R.; Dai, C.; Neuschütz, K.; Fu, G.C. Room-temperature alkyl–alkyl Suzuki cross-coupling of alkyl bromides that possess β-hydrogens. J. Am. Chem. Soc. 2002, doi:10.1002/chin.200205050.
[11]
Stambuli, J.P.; Kuwano, R.; Hartwig, J.F. Unparalleled rates for the activation of aryl chlorides and bromides: Coupling with amines and boronic acids in minutes at room temperature. Angew. Chem. Int. Ed. 2002, 41, 4746–4748, doi:10.1002/anie.200290036.
[12]
Arduengo, A.J., III; Harlow, R.L.; Kline, M. A stable crystalline carbene. J. Am. Chem. Soc. 1991, 113, 361–363.
[13]
Herrmann, W.A.; Elison, M.; Fischer, J.; K?cher, C.; Artus, G.R.J. Metal complexes of N-heterocyclic carbenes—a new structural principle for catalysts in homogeneous catalysis. Angew. Chem. Int. Ed. Engl. 1995, 34, 2371–2374, doi:10.1002/anie.199523711.
[14]
Herrmann, W.A. N-heterocyclic carbenes: A new concept in organometallic catalysis. Angew. Chem. Int. Ed. 2002, 41, 1290–1309, doi:10.1002/1521-3773(20020415)41:8<1290::AID-ANIE1290>3.0.CO;2-Y.
[15]
Scott, N.M.; Clavier, H.; Mahjoor, P.; Stevens, E.D.; Nolan, S.P. Synthetic, structural, and thermochemical studies of N-heterocyclic carbene (NHC) and tertiary phosphine ligands in the [(L)2Ni(CO)2] (L = PR3, NHC) system. Organometallics 2008, 27, 3181–3186.
[16]
Lee, M.-T.; Hu, C.-H. Density functional study of N-heterocyclic and diamino carbene complexes: Comparison with phosphines. Organometallics 2004, 23, 976–983.
[17]
Colacino, E.; Martinez, J.; Lamaty, F. Preparation of NHC-ruthenium complexes and their catalytic activity in metathesis reaction. Coord. Chem. Rev. 2007, 251, 726–764.
[18]
Gade, L.H.; César, V.; Bellemin-Laponnaz, S. A modular assembly of chiral oxazolinylcarbene-rhodium complexes: Efficient phosphane-free catalysts for the asymmetric hydrosilylation of dialkyl ketones. Angew. Chem. Int. Ed. 2004, 43, 1014–1017, doi:10.1002/anie.200353133.
Alonso, F.; Beletskaya, I.P.; Yus, M. Non-conventional methodologies for transition-metal catalysed carbonecarbon coupling: A critical overview. Part 2: The Suzuki reaction. Tetrahedron 2008, 64, 3047–3101, doi:10.1016/j.tet.2007.12.036.
[23]
Herrmann, W.A.; Reisinger, C.P.; Spiegler, M. Chelating N-heterocyclic carbene ligands in palladium-catalyzed Heck-type reactions. J. Organomet. Chem. 1998, 557, 93–96.
[24]
Kim, J.-H.; Kim, J.-W.; Shokouhimehr, M.; Lee, Y.-S. Polymer-supported N-heterocyclic carbene-palladium complex for heterogeneous Suzuki cross-coupling reaction. J. Org. Chem. 2005, 70, 6714–6720.
[25]
Schneider, S.K.; Herrmann, W.A.; Herdtweck, E. Active catalysts for the Suzuki coupling: Palladium complexes of tetrahydropyrimid-2-ylidenes. J. Mol. Catal. A Chem. 2006, 245, 248–254, doi:10.1016/j.molcata.2005.08.046.
[26]
Navarro, O.; Kelly, R.A.; Nolan, S.P. 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. J. Am. Chem. Soc. 2003, 125, 16194–16195, doi:10.1021/ja038631r.
[27]
Marion, N.; Navarro, O.; Mei, J.; Stevens, E.D.; Scott, N.M.; Nolan, S.P. Modified (NHC)Pd(allyl)Cl (NHC=N-heterocyclic carbene) complexes for room-temperature Suzuki-Miyaura and Buchwald-Hartwig reactions. J. Am. Chem. Soc. 2006, 128, 4101–4111.
[28]
Kantchev, E.A.B.; óBrien, C.J.; Organ, M.G. Palladium complexes of N-heterocyclic carbenes as catalysts for cross-coupling reactions—a synthetic chemist’s perspective. Angew. Chem. Int. Ed. 2007, 46, 2768–2813, doi:10.1002/anie.200601663.
Jiang, L.; Li, Z.N.; Zhao, D.F. Progress in the Heck reaction and Suzuki reaction catalyzed by Pd-N-heterocyclic carbene complexes. Chin. J. Org. Chem. 2010, 30, 200–210.
[31]
Türkmen, H.; Pelit, L.; ?etinkaya, B. Water-soluble cis-[(NHC)PdBr2(TPPTS)] catalysts and their applications in Suzuki-Miyaura coupling of aryl chlorides. J. Mol. Catal. A Chem. 2011, 348, 88–93, doi:10.1016/j.molcata.2011.08.008.
[32]
Godoy, F.; Segarra, C.; Poyatos, M.; Peris, E. Palladium catalysts with sulfonate-functionalized-NHC ligands for Suzuki-Miyaura cross-coupling reactions in water. Organometallics 2011, 30, 684–688.
[33]
Dible, B.R.; Cowley, R.E.; Holland, P.L. Remote substitution on N-heterocyclic carbenes heightens the catalytic reactivity of their palladium complexes. Organometallics 2011, 30, 5123–5132.
Netland, K.A.; Krivokapic, A.; Schr?der, M.; Boldt, K.; Lundvall, F.; Tilset, M. Synthesis, X-ray structures, and catalytic applications of palladium(II) complexes bearing N-heterocyclic iminocarbene ligands. J. Organomet. Chem. 2008, 693, 3703–3710, doi:10.1016/j.jorganchem.2008.09.006.
[39]
Yang, C.; Lee, H.M.; Nolan, S.P. Highly efficient Heck reactions of aryl bromides with n-butyl acrylate mediated by a palladium/phosphine-imidazolium salt system. Org. Lett. 2001, 3, 1511–1514, doi:10.1021/ol015827s.
[40]
Wang, J.-W.; Meng, F.-H.; Zhang, L.-F. Suzuki coupling reaction of aryl halides catalyzed by an N-heterocyclic carbene-PdCl2 species based on a porphyrin at room temperature. Organometallics 2009, 28, 2334–2337, doi:10.1021/om800870b.
[41]
Zhang, X.; Qiu, Y.; Rao, B.; Luo, M. Palladium(II)?N-heterocyclic carbene metallacrown ether complexes: Synthesis, structure, and catalytic activity in the Suzuki-Miyaura reaction. Organometallics 2009, 28, 3093–3099.
[42]
Yuan, D.; Huynh, H.V. Dinuclear and tetranuclear palladium(II) complexes of a thiolato-functionalized, benzannulated N-heterocyclic carbene ligand and their activities toward Suzuki-Miyaura coupling. Organometallics 2010, 29, 6020–6027, doi:10.1021/om1008023.
[43]
Shan, F.J.; Jiang, L.; Li, Z.N.; Zhao, D.F. Asymmetric conjugate addition to cyclic enone catalyzed by Cu-NHC complexes with C2 symmetry. Chin. J. Chem. 2011, 29, 973–977, doi:10.1002/cjoc.201190198.
[44]
Navarro, O.; Kaur, H.; Mahjoor, P.; Nolan, S.P. Cross-coupling and dehalogenation reactions catalyzed by (N-heterocyclic carbene)Pd(allyl)Cl complexes. J. Org. Chem. 2004, 69, 3173–3180, doi:10.1021/jo035834p.
[45]
Watanabe, T.; Miyaura, N.; Suzuki, A. Synthesis of sterically hindered biaryls via the palladium-catalyzed cross-coupling reaction of arylboronic acids or their esters with haloarenes. Synlett 1992, 3, 207–210.
[46]
Zhou, W.-J.; Wang, K.-H.; Wang, J.-X. Atom-efficient, palladium-catalyzed Stille coupling reactions of tetraphenylstannane with aryl iodides or aryl bromides in polyethylene glycol 400 (PEG-400). Adv. Synth. Catal. 2009, 351, 1378–1382, doi:10.1002/adsc.200800754.
[47]
Zhou, W.-J.; Wang, K.-H.; Wang, J.-X. Pd(PPh3)4-PEG 400 catalyzed protocol for the atom-efficient Stille cross-coupling reaction of organotin with aryl bromides. J. Org. Chem. 2009, 74, 5599–5602.
[48]
Percec, V.; Golding, G.M.; Smidrkal, J.; Weichold, O. NiCl2(dppe)-catalyzed cross-coupling of aryl mesylates, arenesulfonates, and halides with arylboronic acids. J. Org. Chem. 2004, 69, 3447–3452, doi:10.1021/jo049940i.
[49]
Kylm?l?, T.; Kuuloja, N.; Xu, Y.; Rissanen, K.; Franzén, R. Synthesis of chlorinated biphenyls by Suzuki cross-coupling using diamine or diimine-palladium complexes. Eur. J. Org. Chem. 2008, 4019–4024.
[50]
Schmidt, B.; H?lter, F. Suzuki-Miyaura cross coupling reactions with phenoldiazonium salts. Org. Biomol. Chem. 2011, 9, 4914–4920, doi:10.1039/c1ob05256j.
[51]
Hanada, S.; Yuasa, A.; Kuroiwa, H.; Motoyama, Y.; Nagashima, H. Hydrosilanes are not always reducing agents for carbonyl compounds, II: ruthenium-catalyzed deprotection of tert-butyl groups in carbamates, carbonates, esters, and ethers. Eur. J. Org. Chem. 2010, 6, 1021–1025.
[52]
Fan, X.-H.; Yang, L.-M. NiII–(σ-Aryl) complex catalyzed Suzuki reaction of aryl tosylates with arylboronic acids. Eur. J. Org. Chem. 2010, 13, 2457–2460.
[53]
Diebolt, O.; Braunstein, P.; Nolan, S.P.; Cazin, C.S.J. Room-temperature activation of aryl chlorides in Suzuki–Miyaura coupling using a [Pd(l-Cl)Cl(NHC)]2 complex (NHC = N-heterocyclic carbene). Chem. Commun. 2008, 3190–3192.
[54]
Firouzabadi, H.; Iranpoor, N.; Gholinejad, M. 2-Aminophenyl diphenylphosphinite as an easily accessible ligand for heterogeneous palladium-catalyzed SuzukieMiyaura reaction in water in the absence of any organic co-solvent. J. Organomet. Chem. 2010, 695, 2093–2097.
[55]
Kawai, H.; Kobayashi, Y.; Oi, S.; Inoue, Y. Direct C–H bond arylation of arenes with aryltin reagents catalysed by palladium complexes. Chem. Commun. 2008, 1464–1466.
[56]
Liu, D.; Gao, W.; Dai, Q.; Zhang, X. Triazole-based monophosphines for Suzuki-Miyaura coupling and amination reactions of aryl chlorides. Org. Lett. 2005, 7, 4907–4910, doi:10.1021/ol051844w.
[57]
Wolfe, J.P.; Singer, R.A.; Yang, B.H.; Buchwald, S.L. Highly active palladium catalysts for Suzuki coupling reactions. J. Am. Chem. Soc. 1999, 121, 9550–9561, doi:10.1021/ja992130h.
[58]
Thomas, A.; Anilkumar, G.; Nair, V. Photolytic double decarbonylation route to highly substituted indenes and benzene derivatives. Tetrahedron 1996, 52, 2481–2488, doi:10.1016/0040-4020(95)01069-6.
[59]
Karami, K.; Rizzoli, C.; Salah, M.M. Synthesis and application of ortho-palladated complex of (4-phenylbenzoylmethylene)triphenylphosphorane as a highly active catalyst in the Suzuki cross-coupling reaction. J. Organomet. Chem. 2011, 696, 940–945.
[60]
Pe?a-López, M.; Ayán-Varela, M.; Sarandeses, L.A.; Sestelo, J.P. Palladium-catalyzed cross-coupling reactions of organogold(I) reagents with organic electrophiles. Chem. Eur. J. 2010, 16, 9905–9909, doi:10.1002/chem.201000726.
[61]
Pal, A.; Ghosh, R.; Adarsh, N.N.; Sarkar, A. Pyrazole-tethered phosphine ligands for Pd(0): useful catalysts for Stille, Kumada and Hiyama cross-coupling reactions. Tetrahedron 2010, 66, 5451–5458, doi:10.1016/j.tet.2010.05.026.
[62]
Zhu, L.; Duquette, J.; Zhang, M. An improved preparation of arylboronates: Application in one-pot Suzuki biaryl synthesis. J. Org. Chem. 2003, 68, 3729–3732, doi:10.1021/jo0269114.
[63]
Wu, L.; Li, Z.-W.; Zhang, F.; He, Y.-M.; Fan, Q.-H. Air-stable and highly active dendritic phosphine oxide-stabilized palladium nanoparticles: preparation, characterization and applications in the carbon-carbon bond formation and hydrogenation reactions. Adv. Synth. Catal. 2008, 350, 846–862, doi:10.1002/adsc.200700441.