Fluoride-Promoted Cross-Coupling Reactions of Alkenylsilanols. Elucidation of the Mechanism through Spectroscopic and Kinetic Analysis

Journal of the American Chemical Society

Volumn 126, Issue 15, 2004, Pages 4865-4875

  Denmark, Scott E ^a   Sweis, Ramzi F ^a   Wehrli, Daniel ^a  

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

Author keywords

[No Author keywords available]

Indexed keywords

AMMONIUM COMPOUNDS; CONCENTRATION (PROCESS); HYDROGEN BONDS; PALLADIUM; REACTION KINETICS; SOLUTIONS; SPECTROSCOPIC ANALYSIS;

ALKENYLSILANOLS; CROSS-COUPLING REACTIONS; KINETIC ANALYSIS; TRANSMETALATION;

SILICON COMPOUNDS;

2 IODOTHIOPHENE; ALCOHOL DERIVATIVE; ALKENYL GROUP; DIISOPROPYL (1 HEPTENYL)SILANOL; DIMETHYL (1 HEPTENYL)SILANOL; FLUORIDE; IODIDE; IODINE DERIVATIVE; ORGANOSILICON DERIVATIVE; PALLADIUM; SILANE DERIVATIVE; SILICON; TETRABUTYLAMMONIUM; THIOPHENE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL REACTION KINETICS; CONCENTRATION (PARAMETERS); CROSS COUPLING REACTION; DISSOLUTION; ENERGY; HYDROGEN BOND; METAL BINDING; OXIDATION; REACTION ANALYSIS; SPECTROSCOPY;

HYDROGEN BONDING; KINETICS; MAGNETIC RESONANCE SPECTROSCOPY; PALLADIUM; QUATERNARY AMMONIUM COMPOUNDS; SILANES; THIOPHENES;

EID: 1842862944     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja037234d     Document Type: Article

References (62)

1. Metal-Catalyzed Cross-Coupling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH: Weinheim, Germany, 1998.
2. (a) Tamao, K.; Sumitani, K.; Kumada, M. J. Am. Chem. Soc. 1972, 94, 4374.
3. (b) Corriu, R. J. P.; Masse, J. P. J. Chem. Soc., Chem. Commun. 1972, 144.
4. Reviews (a) Denmark, S. E.; Sweis, R. F. Acc. Chem. Res. 2002, 35, 835.
5. (b) Denmark, S. E.; Sweis, R. F. Chem. Pharm. Bull. 2002, 50, 1531.
6. (c) Denmark, S. E.; Ober, M. H. Aldrichimica Acta 2003, 36 (3), 75.
7. (a) Stille, J. K. Angew. Chem., Int. Ed. Engl. 1986, 25, 508.
8. (b) Farina, V.; Krishnamurthy, V.; Scott, W. J. Org. React. 1998, 50, 1.
9. (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
10. (b) Suzuki, A. J. Organomet. Chem. 1999, 576, 147.
11. (c) Miyaura, N. Top. Curr. Chem. 2002, 219, 11.
12. (d) Suzuki, A. In Metal-catalyzed Cross-coupling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH: Weinhein, Germany, 1998; Chapter 2.
13. Farina, V.; Krishnan, B. J. Am. Chem. Soc. 1991, 113, 9585.
14. (a) Amatore, C.; Jutand, A. J. Organomet. Chem. 1999, 576, 254.
15. (b) Amatore, C.; Jutand, A. Acc. Chem. Res. 2000, 33, 314.
16. Casado, A. L.; Espinet, P. J. Am. Chem. Soc. 1998, 120, 8978.
17. (b) Casado, A. L.; Espinet, P.; Gallego, A. M. J. Am. Chem. Soc. 2000, 122, 11771.
18. Woerpel, K. A.; Ridgeway, B. H. J. Org. Chem. 1998, 63, 458.
19. Matos, K.; Soderquist, J. A. J. Org. Chem. 1998, 63, 461.
20. The mechanism of palladium-catalyzed aminations has also been the focus of several in-depth mechanistic investigations. See: (a) Singh, U. K.; Strieter, E. R.; Blackmond, D. G.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 14104.
21. (b) Alcazar-Roman, L. M.; Hartwig, J. F.; Reingold, A. L.; Liable-Sands, L. M.; Guzei, I. A. J. Am. Chem. Soc. 2000, 122, 4618.
22. E′-type transmetalations that can be influenced by solvent, catalyst ligands, and temperature, See: (a) Hatanaka, Y. ; Hiyama, T. J. Am. Chem. Soc. 1990, 112, 7793.
23. (b) Hatanaka, Y.; Goda, K.; Hiyama, T. Tetrahedron Lett. 1994, 35, 6511.
24. Ohmura, H.; Matsuhashi, H.; Tanaka, M.; Kuroboshi, M.; Hiyama, T.; Hatanaka, Y.; Goda, G. J. Organomet. Chem. 1995, 499, 167.
25. Isolable pentacoordinate fluorosilicates were demonstrated to undergo cross-coupling reactions prior to this breakthrough. Yoshida, J.; Tamao, K.; Yamamoto, H.; Kakui, T.; Uchida, T.; Kumada, M. Organometallics 1982, 1, 542.
26. (a) Hatanaka, Y.; Hiyama, T. J. Org. Chem. 1988, 53, 918.
27. (b) Hatanaka, Y.; Hiyama, T. J. Org. Chem. 1989, 54, 270.
28. For a review on advances in palladium-catalyzed coupling reaction to aryl chlorides, see: Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 4176.
29. Denmark, S. E.; Wehrli, D. Org. Lett. 2000, 2, 565.
30. Denmark, S. E.; Choi, J. Y. J. Am. Chem. Soc. 1999, 121, 5821.
31. Denmark, S. E.; Wehrli, D.; Choi, J. Y. Org. Lett. 2000, 2, 2491.
32. 29Si resonance position upon addition of TBAF; see Figure 4.
33. It should be pointed out that the ratios of disiloxane and "unknowns" in Figure 5 represent equilibrium values obtained by independent NMR analysis. Under normal conditions, the rate of reaction is competitive with the rate of establishing these equilibria, so that the actual ratios may not reflect the ratios during a cross-coupling reaction.
34. The typical chemical shift range for tetracoordinate silicon is δ +30 to -30 ppm, and for pentacoordinate silicon it is δ -75 to -130 ppm. Takeuchi, Y.; Takayama, T. In The Chemistry of Organic Silicon Compounds; Rappoport, Z., Apeloig, Y., Eds.; John Wiley: Chichester, U.K., 1998; Chapter 6, Vol. 2, Part 1.
35. Sharma, R. K.; Fry, J. L. J. Org. Chem. 1983, 48, 2112.
36. (a) Fujiwara, F. Y.; Martin, J. S. J. Am. Chem. Soc. 1974, 96, 7625.
37. (b) Fujiwara, F. Y.; Martin, J. S. J. Am. Chem. Soc. 1974, 96, 7632
38. (c) Landini, D.; Molinari, H.; Penso, M.; Rampoldi, A. Synthesis 1988, 953.
39. (d) Cox, D. P.; Terpinski, J.; Lawrynowicz, W. J. Org. Chem. 1984, 49, 3216.
40. - at -80 °C, ref 22.
41. Further attempts to provide spectroscopic support for (E)-14 as the structure of X involved heteronuclear NOE experiments between the hydrogen resonance at 5.05 ppm and the fluorine resonances for TBAF (ca. 117 ppm) and X (ca. 150 ppm). Although weak NOE signals could be detected, the interpretation was ambiguous due to the water of hydration from the TBAF sample.
42. Clearly, the reaction order is not affected by the steric demand of the pendant alkyl groups on the silanol. Quantitative studies also have shown that, under fluoride activation, (E)-1 and (E)-2 have nearly identical coupling rates. Denmark, S. E.; Neuville, L.; Christy, M. E. L. Unpublished results from these laboratories.
43. 2 = 0.96701).
44. The first-order rate constant was obtained by fitting to the slope of a plot of log[conversion] against time.
45. -1, ΔH = 14.87 kcal/mol, ΔS = -5.14 eu, and ΔG = 16.38 kcal/mol.
46. Hiyama, T. In Metal-Catalyzed Cross-Coupling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH: Weinheim, Germany, 1998; Chapter 10.
47. (a) Emsley, J. Chem. Soc. Rev. 1980, 9, 91.
48. (b) Emsley, J. Rev. Inorg. Chem. 1981, 3, 105.
49. (c) Clark, J. H.; Goodman, E. M.; Smith, D. K.; Brown, S. J.; Miller, J. M. J. Chem. Soc., Chem. Commun. 1986, 657.
50. The oxidative insertion step of palladium-catalyzed cross-coupling has been studied extensively. (a) Amatore, C.; Bucaille, A.; Fuxa, A.; Jutand, A.; Meyer, G.; Ntepe, A. N. Chem.-Eur. J. 2001, 7, 2134.
51. (b) Amatore, C.; Jutand, A.; Thuilliez, A. Organometallics 2001, 20, 3241.
52. (c) Amatore, C.; Jutand, A.; Suarez, A. J. Am. Chem. Soc. 1993, 115, 9531.
53. (d) Jutand, A.; Mosleh, A. Organometallics 1995, 14, 1810.
54. (e) Jutand, A.; Mosleh, A. Organometallics 1995, 14, 1818.
55. It is important to note that a rate equation reveals information regarding the mechanistic pathway from the lowest energy species to the highest transition state. Hence, the inverse order dependence of TBAF lends further support to the existence of (E)-14.
56. It should be clear that, if the disiloxane were the resting state throughout, that eventually a saturation regime in the TBAF dependence would be reached and zeroth-order behavior would be displayed.
57. Denmark, S. E.; Neuville, L. Org. Lett. 2000, 2, 3221.
58. Hosoi, K.; Nozaki, K.; Hiyama, T. Chem. Lett. 2002, 138.
59. (a) Itami, K.; Nokami, T.; Yoshida, J. J. Am. Chem. Soc. 2001, 123, 5600.
60. (b) Itami, K.; Nokami, T.; Ishimura, Y.; Mitsudo, K.; Kamei, T.; Yoshida, J. J. Am. Chem. Soc. 2001, 123, 11577.
61. Trost, B. M.; Machacek, M. R.; Ball, Z. T. Org. Lett. 2003, 5, 1895.
62. Denmark, S. E.; Sweis, R. F. J. Am. Chem. Soc. 2001, 123, 6439.