铁催化芳基格氏试剂的联芳交叉偶联的反应机理

doi:10.3866/PKU.WHXB201503026

Abstract

Abstract:

Mechanisms for the [Fe(MgBr)₂] catalyzed cross-coupling reaction between ortho-chlorostyrene and phenylmagnesium bromide to form biaryl were studied using density functional theory (DFT) calculations. We investigated two mechanisms. Cycle A included three basic steps: (I) oxidation of [Fe(MgBr)₂] to obtain [Ar- Fe(MgBr)], (II) addition to yield [Ar-(phenyl)-Fe(MgBr)₂], and (III) reductive elimination to return to [Fe(MgBr)₂]. Cycle B did not form [Ar-Fe(MgBr)]. In the first step, phenylmagnesium bromide attacks the intermediate of the oxidative addition directly before [Cl-Mg-Br] dissociates to form [Ar-Fe(MgBr)]. The catalytic Cycle B is favored over the catalytic Cycle Awhen considering the solvent effect. The rate-limiting step in the overall catalytic cycle for both Cycle A and Cycle B is the reductive elimination of [Ar-(phenyl)-Fe(MgBr)₂] to regenerate the catalyst [Fe(MgBr)₂], where the Gibbs free energy in solvent tetrahydrofuran (THF), ΔG_sol, is 82.98 kJ ·mol^-1, as determined using the conductor polarized continuum model (CPCM) method.

Key words: Iron catalyst, Biaryl, Cross-coupling, Reaction mechanism, Density functional theory

MSC2000:

O641

Click here to download Supporting Info material in PDF type

REN Qing-Hua, SHEN Xiao-Yan. Reaction Mechanism for the Iron-Catalyzed Biaryl Cross-Coupling of Aryl Grignard Reagents[J].Acta Phys. -Chim. Sin., 2015, 31(5): 852-858.

References

(1) Negishi, E. Accounts Chem. Res. 1982, 15, 340. doi: 10.1021/ar00083a001
(2) Yang, Y.; Oldenhuis, N. J.; Buchwald, S. L. Angew. Chem. Int. Edit. 2013, 125, 643. doi: 10.1002/ange.201207750
(3) Blangetti, M.; Rosso, H.; Prandi, C.; Deagostino, A.; Venturello, P. Molecules 2013, 18, 1188. doi: 10.3390/molecules18011188
(4) Miyaura, N.; Suzuki, A. J. Chem. Soc. Chem. Commun. 1979, 19, 866. doi: 10.1039/C39790000866
(5) Heck, R. F.; Nolley, J. P. J. Org. Chem. 1972, 37, 2320. doi: 10.1021/jo00979a024
(6) Cabri, W.; Candiani, I. Accounts Chem. Res. 1995, 28, 2. doi: 10.1021/ar00049a001
(7) Milstein, D.; Stille, J. K. J. Am. Chem. Soc. 1978, 100, 3636. doi: 10.1021/ja00479a077
(8) Yabe, Y.; Maegawa, T.; Monguchi, Y.; Sajiki, H. Tetrahedron 2010, 66, 8654. doi: 10.1016/j.tet.2010.09.027
(9) Tamao, K.; Sumitani, K.; Kumada, M. J. Am. Chem. Soc. 1972, 94, 4374. doi: 10.1021/ja00767a075
(10) Yang, L. M.; Huang, L. F.; Luh, T. Y. Org. Lett. 2004, 6, 1461. doi: 10.1021/ol049686g
(11) Vechorkin, O.; Proust, V.; Hu, X. J. Am. Chem. Soc. 2009, 131, 9756. doi: 10.1021/ja9027378
(12) Torssell, K. B. Natural Product Chemistry: a Mechanistic and Biosynthetic Approach to Secondary Metabolism; JohnWiley & Sons: New Jersey, 1983; p 401.
(13) Hassan, J.; Sevignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M. Chem. Rev. 2002, 102, 1359. doi: 10.1021/cr000664r
(14) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457. doi: 10.1021/cr00039a007
(15) Bringmann, G.; Mortimer, A. J. P.; Keller, P. A.; Gresser, M. J.; Garner, J.; Breuning, M. Angew. Chem. Int. Edit. 2005, 44, 5384.
(16) Kirsch, P.; Bremer, M. Angew. Chem. Int. Edit. 2000, 39, 4216.
(17) Bauer, E. B. Curr. Org. Chem. 2008, 12, 1341. doi: 10.2174/ 138527208786241556
(18) Bolm, C.; Legros, J.; Paih, J. L.; Zani, L. Chem. Rev. 2004, 104, 6217. doi: 10.1021/cr040664h
(19) Czaplik, W. M.; Mayer, M.; Cvengros, J.; vonWangelin, A. J. ChemSusChem 2009, 2, 396. doi: 10.1002/cssc.v2:5
(20) Sherry, B. D.; Furstner, A. Accounts Chem. Res. 2008, 41, 1500. doi: 10.1021/ar800039x
(21) Furstner, A.; Leitner, A. Angew. Chem. Int. Edit. 2002, 41, 609.
(22) Furstner, A.; Leitner, A.; Mendez, M.; Krause, H. J. Am. Chem. Soc. 2002, 124, 13856. doi: 10.1021/ja027190t
(23) Correa, A.; Mancheno, O. G.; Bolm, C. Chem. Soc. Rev. 2008, 37, 1108. doi: 10.1039/b801794h
(24) Furstner, A.; Martin, R. Chem. Lett. 2005, 34, 624. doi: 10.1246/cl.2005.624
(25) Furstner, A.; Martin, R.; Krause, H.; Seidel, G.; Goddard, R.; Lehmann, C.W. J. Am. Chem. Soc. 2008, 130, 8773. doi: 10.1021/ja801466t
(26) Noda, D.; Sunada, Y.; Hatakeyama, T.; Nakamura, M.; Nagashima, H. J. Am. Chem. Soc. 2009, 131, 6078. doi: 10.1021/ja901262g
(27) Scheiper, B.; Bonnekessel, M.; Krause, H.; Furstner, A. J. Org. Chem. 2004, 69, 3943. doi: 10.1021/jo0498866
(28) Molander, G. A.; Rahn, B. J.; Shubert, D. C. Tetrahedron Lett. 1983, 24, 5449. doi: 10.1016/S0040-4039(00)94109-1
(29) Quintin, J.; Franck, X.; Hocquemiller, R.; Figadere, B. Tetrahedron Lett. 2002, 43, 3547. doi: 10.1016/S0040-4039(02)00568-3
(30) Hocek, M.; Dvorakova, H. J. Org. Chem. 2003, 68, 5773. doi: 10.1021/jo034351i
(31) Hatakeyama, T.; Nakamura, M. J. Am. Chem. Soc. 2007, 129, 9844. doi: 10.1021/ja073084l
(32) Hatakeyama, T.; Hashimoto, S.; Ishizuka, K.; Nakamura, M. J. Am. Chem. Soc. 2009, 131, 11949. doi: 10.1021/ja9039289
(33) Mayer, M.; Welther, A.; vonWangelin, A. J. ChemCatChem 2011, 3, 1567. doi: 10.1002/cctc.v3.10
(34) Clayton, H. S.; Moss, J. R.; Dry, M. E. J. Organomet. Chem. 2003, 688, 181. doi: 10.1016/j.jorganchem.2003.08.044
(35) Knolker, H. J. Chem. Soc. Rev. 1999, 28, 151. doi: 10.1039/a705401g
(36) Gulak, S.; vonWangelin, A. J. Angew. Chem. Int. Edit. 2012, 51, 1357. doi: 10.1002/anie.201106110
(37) Smith, R. S.; Kochi, J. K. J. Org. Chem. 1976, 41, 502. doi: 10.1021/jo00865a019
(38) Bogdanovic, B.; Schwickardi, M. Angew. Chem. Int. Edit. 2000, 39, 4610.
(39) Kleimark, J.; Hedstrom A.; Larsson P. F.; Johansson, C.; Norrby, P. ChemCatChem 2009, 1, 152. doi: 10.1002/cctc.v1:1
(40) Ren, Q.; Guan, S.; Jiang, F.; Fang, J. J. Phys. Chem. A 2013, 117, 756. doi: 10.1021/jp3045498
(41) Czaplik, W. M.; Mayer, M.; vonWangelin, A. J. ChemCatChem 2011, 3, 135. doi: 10.1002/cctc.201000276
(42) Mo, Z.; Zhang, Q.; Deng, L. Organometallics 2012, 31, 6518. doi: 10.1021/om300722g
(43) Becke, A. D. Phys. Rev. A 1988, 38, 3098. doi: 10.1103/PhysRevA.38.3098
(44) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
(45) Hertwig, R. H.; Koch, W. Chem. Phys. Lett. 1997, 268, 345. doi: 10.1016/S0009-2614(97)00207-8
(46) Lee, C. T.; Yang, W. T.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785
(47) Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623. doi: 10.1021/j100096a001
(48) Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200. doi: 10.1139/p80-159
(49) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03, Revision C.02; Gaussian Inc.; Wallingford, CT, 2004.
(50) Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J. Chem. Phys. 1980, 72, 650. doi: 10.1063/1.438955
(51) McLean, A. D.; Chandler, G. S. J. Chem. Phys. 1980, 72, 5639. doi: 10.1063/1.438980
(52) Andrae, D.; Haussermann, U.; Dolg, M.; Stoll, H.; Preuss, H. Theor. Chim. Acta. 1990, 77, 123. doi: 10.1007/BF01114537
(53) Cossi, M.; Rega, N.; Scalmani, G.; Barone, V. J. Comput. Chem. 2003, 24, 669. doi: 10.1002/jcc.10189
(54) Castejon, H.; Wiberg, K. B. J. Am. Chem. Soc. 1999, 121, 2139. doi: 10.1021/ja983736t
(55) Perng, B. C.; Newton, M. D.; Raineri, F. O.; Friedman, H. L. J. Chem. Phys. 1996, 104, 7153 and 7177.
(56) Najafi, M.; Zahedi, M.; Klein, E. Comput. Theor. Chem. 2011, 978, 16. doi: 10.1016/j.comptc.2011.09.014
(57) Schubert, G.; Papai, I. J. Am. Chem. Soc. 2003, 125, 14847. doi: 10.1021/ja035791u
(58) Belelli, P. G.; Damiani, D. E.; Castellani, N. J. Chem. Phys. Lett. 2005, 401, 515. doi: 10.1016/j.cplett.2004.11.089
(59) Feng, J.; Ren, Q. H. Acta. Phys. -Chim. Sin. 2014, 30, 821. [蒋峰, 任清华. 物理化学学报, 2014, 30, 821.]
(60) Nova, A.; Ujaque, G.; Maseras, F.; Liedos, A.; Espinet, P. J. Am. Chem. Soc. 2006, 128, 14571. doi: 10.1021/ja0635736

[1]	Dan WANG,Xunlei DING,Henglu LIAO,Jiayu DAI. Methane Activation on (Au/Ag)₁-Doped Vanadium Oxide Clusters [J]. Acta Physico-Chimica Sinica, 2019, 35(9): 1005-1013.
[2]	Yuanyuan HU,Congyang WANG. Bimetallic C―H Activation in Homogeneous Catalysis [J]. Acta Physico-Chimica Sinica, 2019, 35(9): 913-922.
[3]	Qiang CHEN,Li-Xue JIANG,Hai-Fang LI,Jiao-Jiao CHEN,Yan-Xia ZHAO,Sheng-Gui HE. Thermal Activation of Methane by Diatomic Vanadium Boride Cations [J]. Acta Physico-Chimica Sinica, 2019, 35(9): 1014-1020.
[4]	Qingbing WANG,Zhengwei GUO,Gong CHEN,Gang HE. DPPF-Mediated C―H Arylation of Arenes with Aryl Iodides for Synthesis of Biaryl Linkages [J]. Acta Physico-Chimica Sinica, 2019, 35(9): 1021-1026.
[5]	Mengru HAN,Yanan ZHOU,Xuan ZHOU,Wei CHU. Tunable Reactivity of MNi₁₂ (M = Fe, Co, Cu, Zn) Nanoparticles Supported on Graphitic Carbon Nitride in Methanation [J]. Acta Physico-Chimica Sinica, 2019, 35(8): 850-857.
[6]	Lu WANG,Wei SUN,Chao LIU. Homodinuclear Ferrous Group Metal Complexes and Their Application in Homogeneous Catalysis [J]. Acta Phys. -Chim. Sin., 2019, 35(7): 697-708.
[7]	Yue ZHAO,Jiatong CUI,Jichuang HU,Jiabi MA. Reactivities of VO_1–4⁺ Toward n-C_mH_2m+2 (m = 3, 5, 7) as Functions of Oxygen Content and Carbon Chain Length [J]. Acta Phys. -Chim. Sin., 2019, 35(5): 531-538.
[8]	Bihua CHEN,H. M. ELAGEED Elnazeer,Yongya ZHANG,Guohua GAO. BmmimOAc-Catalyzed Direct Condensation of 2-(Arylamino) Alcohols to Synthesize 3-Arylthiazolidine-2-thiones [J]. Acta Phys. -Chim. Sin., 2018, 34(8): 952-958.
[9]	Martínez GONZÁLEZ Marco,Carlos CÁRDENAS,Juan I. RODRÍGUEZ,Shubin LIU,Farnaz HEIDAR-ZADEH,Ramón Alain MIRANDA-QUINTANA,Paul W. AYERS. Quantitative Electrophilicity Measures [J]. Acta Phys. -Chim. Sin., 2018, 34(6): 662-674.
[10]	Paul W. AYERS,Mel LEVY. Levy Constrained Search in Fock Space: An Alternative Approach to Noninteger Electron Number [J]. Acta Phys. -Chim. Sin., 2018, 34(6): 625-630.
[11]	Tian LU,Qinxue CHEN. Revealing Molecular Electronic Structure via Analysis of Valence Electron Density [J]. Acta Phys. -Chim. Sin., 2018, 34(5): 503-513.
[12]	Farnaz HEIDAR-ZADEH,Paul W. AYERS. Generalized Hirshfeld Partitioning with Oriented and Promoted Proatoms [J]. Acta Phys. -Chim. Sin., 2018, 34(5): 514-518.
[13]	Yueqi YIN,Mengxu JIANG,Chunguang LIU. DFT Study of POM-Supported Single Atom Catalyst (M₁/POM, M = Ni, Pd, Pt, Cu, Ag, Au, POM = [PW₁₂O₄₀]^3-) for Activation of Nitrogen Molecules [J]. Acta Phys. -Chim. Sin., 2018, 34(3): 270-277.
[14]	Fanhua YIN,Kai TAN. Density Functional Theory Study on the Formation Mechanism of Isolated-Pentagon-Rule C₁₀₀(417)Cl₂₈ [J]. Acta Phys. -Chim. Sin., 2018, 34(3): 256-262.
[15]	Robert C MORRISON. Fukui Functions for the Temporary Anion Resonance States of Be^-, Mg^-, and Ca^- [J]. Acta Phys. -Chim. Sin., 2018, 34(3): 263-269.

Reaction Mechanism for the Iron-Catalyzed Biaryl Cross-Coupling of Aryl Grignard Reagents

PDF (PC)

Like

Knowledge

Abstract

Supporting Info

Cite this article

share this article

References

Related Articles 15

Metrics

Comments

Recommended 10