Citation: REN Qing-Hua, SHEN Xiao-Yan. Reaction Mechanism for the Iron-Catalyzed Biaryl Cross-Coupling of Aryl Grignard Reagents[J]. Acta Physico-Chimica Sinica, ;2015, 31(5): 852-858. doi: 10.3866/PKU.WHXB201503026 shu

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

1.
Department of Chemistry, College of Science, Shanghai University, Shanghai 200444, P. R. China

Received Date: 25 December 2014
Available Online: 2 March 2015
Fund Project: 项目(B.58-B111-12-101, B.58-B111-12-103)资助 (B.58-B111-12-101, B.58-B111-12-103)

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