Mechanistic duality in palladium-catalyzed cross-coupling reactions of aryldimethylsilanolates. Intermediacy of an 8-Si-4 arylpalladium(II) silanolate

Journal of the American Chemical Society

Volumn 132, Issue 4, 2010, Pages 1243-1245

  Denmark, Scott E ^a   Smith, Russell C ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; OPTICAL SWITCHES; PALLADIUM; POTASSIUM; SILICON;

A-THERMAL; CATALYTIC CYCLES; CHEMICAL EQUATIONS; FLUOROBENZENE; MECHANISTIC PATHWAYS; PALLADIUM-CATALYZED CROSS-COUPLING REACTIONS; RATE EQUATIONS; SILANOLATES; TRANSMETALATION;

CHEMICAL REACTIONS;

METHYL GROUP; PALLADIUM; PALLADIUM COMPLEX; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; SILANE DERIVATIVE; SILICON; POTASSIUM (4-METHOXYPHENYL)DIMETHYL SILANOLATE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION KINETICS; CROSS COUPLING REACTION; CRYSTAL STRUCTURE; FLUORINE NUCLEAR MAGNETIC RESONANCE; PHOSPHORUS NUCLEAR MAGNETIC RESONANCE; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; CHEMICAL STRUCTURE; CHEMISTRY;

CATALYSIS; MOLECULAR STRUCTURE; PALLADIUM; SILANES;

EID: 77950341146     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja907049y     Document Type: Article

References (32)

1. (a) Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.; de Meijere, A., Diederich, F., Eds.; Wiley-VCH: Weinheim, 2004.
2. (b) Handbook of Organopalladium Chemistry; Negishi, E., Ed.; Wiley-Interscience: New York, 2002.
3. (a) Jutand, A. Chem. Rev. 2008, 108, 2300-2347.
4. (b) Espinet, P.; Echavarren, A. M. Angew. Chem., Int. Ed. 2004, 43, 4704-4734.
5. Hatanaka, Y.; Hiyama, T. J. Am. Chem. Soc. 1990, 112, 7793-7794.
6. (a) Matos, K.; Soderquist, J. A. J. Org. Chem. 1998, 63, 461-470.
7. (b) Ridgway, B. H.; Woerpel, K. A. J. Org. Chem. 1998, 63, 458-460.
8. (c) Braga, A. A. C.; Morgon, N. H.; Ujaque, G.; Lledós, A.; Maseras, F. J. Organomet. Chem. 2006, 691, 4459-4466.
9. (d) Braga, A. A. C.; Ujaque, G.; Maseras, F. Organometallics 2006, 25, 3647-3658.
10. Hartwig has demonstrated the intermediacy of an Rh-O-B bond in β-aryl eliminations to form Rh-aryl bonds: Zhao, P.; Incarvito, C. D.; Hartwig, J. F. J. Am. Chem. Soc. 2007, 129, 1876-1877.
11. For studies on the transmetalation of organosilanes to platinum, see: (a) Fukuoka, A.; Sato, A.; Kodama, K.; Hirano, M.; Komiya, S. Inorg. Chim. Acta 1999, 294, 266-274.
12. (b) Mintcheva, N.; Nishihara, Y.; Mori, A.; Osakada, K. J. Organomet. Chem. 2001, 629, 61-67.
13. (c) Mintcheva, N.; Nishihara, Y.; Tanabe, M.; Hirabayashi, K.; Mori, A.; Osakada, K. Organometallics 2001, 20, 1243-1246.
14. (a) Denmark, S. E.; Regens, C. S. Acc. Chem. Res. 2008, 41, 1486-1499.
15. Hiyama, T.; Shirakawa, E. Top. Curr. Chem. 2002, 219, 61-85.
16. (a) Denmark, S. E.; Sweis, R. F.; Wehrli, D. J. Am. Chem. Soc. 2004, 126, 4865-4875.
17. (b) Denmark, S. E.; Sweis, R. F. J. Am. Chem. Soc. 2004, 126, 4876-4882.
18. Denmark, S. E.; Ober, M. H. Adv. Synth. Catal. 2004, 346, 1703-1714.
19. Denmark, S. E.; Smith, R. C.; Chang, W.-T.; Muhuhi, J. M. J. Am. Chem. Soc. 2009, 131, 3104-3118.
20. 3P have been established to be the monomeric, T-shaped complexes: (a) Stambuli, J. P.; Incarvito, C. D.; Buhl, M.; Hartwig, J. F. J. Am. Chem. Soc. 2004, 126, 1184-1194.
21. (b) Stambuli, J. P.; Weng, Z.; Incarvito, C. D.; Hartwig, J. F. Angew. Chem., Int. Ed. 2007, 46, 7674-7677.
22. (c) The monomeric form of the palladium(II) silanolate complex correlates well to previously reported palladium(II) alkoxide complexes.
23. All kinetic data and plots are available as Supporting Information.
24. (a) The inability to distinguish the pathways results from the likely saturation of either of these intermediates under catalytic conditions. (b) This rate equation is also consistent with turnover-limiting reductive elimination. However, reductive elimination is known to be extremely rapid with palladium; thus, transmetalation remains the only viable turnover-limiting step: Gillie, A.; Stille, J. K. J. Am. Chem. Soc. 1980, 102, 4933-4941.
25. Dai, C.; Fu, G. J. Am. Chem. Soc. 2001, 123, 2719-2724.
26. Further support for a fast and irreversible displacement was achieved using a systematic titration study. The results of this study are discussed in the Supporting Information.
27. (a) The crystallographic coordinates have been deposited with the Cambridge Crystallographic Data Centre; deposition no. 744109. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre, 12 Union Rd., Cambridge CB2 1EZ, UK; fax (+44) 1223-336-033 or via www.ccdc.cam.ac.uk/conts/retrieving.html or. (b) The crystallographic coordinates have been deposited with the Cambridge Crystallographic Data Centre; deposition no. 645666. This palladium(II) silanolate complex and its reactivity will be reported in due course.
28. Marciniec, B.; Maciejewski, H. Coord. Chem. Rev. 2001, 223, 301-335.
29. The remaining mass balance was confirmed to be the dimerization of the arene derived from the aryl bromide. This product may be a result of an unproductive bimolecular recombination of the palladium(II) silanolate complexes. This amount of homocoupling was not observed under the catalytic condition reported in ref 11 and may be a result of the longer lived pre-transmetalation intermediate under these conditions.
30. Reactions were performed at a lower temperature than for the catalytic reactions to obtain a reliably measurable rate.
31. -. We were unable to identify the saturation point because of the solubility of the silanolate salts.
32. Barrios-Landeros, F.; Carrow, B. P.; Hartwig, J. F. J. Am. Chem. Soc. 2009, 131, 8141-8154.