Mechanism of palladium-catalyzed diene cyclization/hydrosilylation: Direct observation of intramolecular carbometalation

Journal of the American Chemical Society

Volumn 126, Issue 20, 2004, Pages 6332-6346

  Perch, Nicholas S ^a   Widenhoefer, Ross A ^a  

^a DUKE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; CATALYSIS; CATALYSTS; CHEMICAL ANALYSIS; COMPLEXATION;

CYCLIZATION; HYDROSILYLATION;

PALLADIUM;

CARBONYL DERIVATIVE; CHELATE; CYCLOPENTYLMETHYL COMPLEX; DEUTERIUM; DIMETHYL DIALLYLMALONATE; MALONIC ACID DERIVATIVE; PALLADIUM; PALLADIUM COMPLEX; SILANE DERIVATIVE; TRIETHYLSILANE; UNCLASSIFIED DRUG;

ARTICLE; CARBOMETALLATION; CATALYSIS; CYCLIZATION; HYDROSILYLATION; KINETICS; METALLATION; MOLECULAR MECHANICS;

ALKENES; CATALYSIS; CHELATING AGENTS; CYCLIZATION; INDICATORS AND REAGENTS; KINETICS; MAGNETIC RESONANCE SPECTROSCOPY; METALS; PALLADIUM; SILANES;

EID: 2442677765     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja049806f     Document Type: Article

References (99)

1. (a) Hudlicky, T.; Price, J. D. Chem. Rev. 1989, 89, 1467.
2. (b) Trost, B. M. Chem. Soc. Rev. 1982, 11, 141.
3. (a) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635.
4. (b) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49.
5. (c) Trost, B. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 259.
6. (a) Ojima, I.; Donovan, R. J.; Shay, W. R. J. Am. Chem. Soc. 1992, 114, 6580.
7. (b) Muraoka, T.; Matsuda, I.; Itoh, K. Tetrahedron Lett. 1998, 39, 7325.
8. (c) Ojima, I.; Vu, A. T.; Lee, S.-L.; McCullagh, J. V.; Moralee, A. C.; Fujiwara, M.; Hoang, T. H. J. Am. Chem. Soc. 2002, 124, 9164.
9. (d) Molander, G. A.; Retsch, W. H. J. Am. Chem. Soc. 1997, 119. 8817.
10. Chakrapani, H.; Liu, C.; Widenhoefer, R. A. Org. Lett. 2003, 5, 157.
11. (a) Negishi, E.-i.; Jensen, M. D.; Kondakov, D. Y.; Wang, S. J. Am. Chem. Soc. 1994, 116, 8404.
12. (b) Shaughnessy, K. H.; Waymouth, R. M. J. Am. Chem. Soc. 1995, 117, 5873.
13. (c) Molander, G. A.; Hoberg, J. O. J. Am. Chem. Soc. 1992, 114, 3123.
14. (d) Onozawa, S.; Sakakura, T.; Tanaka, M. Tetrahedron Lett. 1994, 35, 8177.
15. (e) Molander, G. A.; Nichols, P. J. J. Am. Chem. Soc. 1995, 117, 4415.
16. (f) Molander, G. A.; Dowdy, E. D.; Schumann, H. J. Org. Chem. 1998, 63, 3386.
17. (g) Molander, G. A.; Corrette, C. P. J. Org. Chem. 1999, 64, 9697.
18. Widenhoefer, R. A. Acc. Chem. Res. 2002, 35, 905.
19. (a) Tamao, K.; Kobayashi, K.; Ito, Y. J. Am. Chem. Soc. 1989, 111, 6478.
20. (b) Tamao, K.; Kobayashi, K.; Ito, Y. Synlett 1992, 539.
21. (a) Madine, J. W.; Wang, X.; Widenhoefer, R. A. Org. Lett. 2001, 3, 385.
22. (b) Wang, X.; Chakrapani, H.; Madine, J. W.; Keyerleber, M. A.; Widenhoefer, R. A. J. Org. Chem. 2002, 67, 2778.
23. (c) Liu, C.; Widenhoefer, R. A. Organometallics 2002, 21, 5666.
24. (a) Obora, Y.; Tsuji, Y.; Kakehi, Kobayashi, M.; Shinkai, Y.; Ebihara, M.; Kawamura, T. J. Chem. Soc., Perkin Trans. 1 1995, 599.
25. (b) Takacs, J. M.; Chandramouli, S. Organometallics 1990, 9, 2877.
26. (c) Takacs, J. M.; Zhu, J.; Chandramouli, S. J. Am. Chem. Soc. 1992, 114, 773.
27. (a) These secondary transformations include the oxidation of organosilanes10b and organoboranes and the cross-coupling of alkenylsilanes,10c alkenylstannanes,10d and organoboranes.10e
28. (b) Jones, G. R.; Landais, Y. Tetrahedron 1996, 52, 7599.
29. (c) Hiyama, T.; Hatanaka, Y. Pure Appl. Chem. 1994, 66, 1471.
30. (d) Mitchell, T. N. Synthesis 1992, 803.
31. (e) Suzuki, A. Pure Appl. Chem. 1991, 63, 419.
32. DeCarli, M. A.; Widenhoefer, R. A. J. Am. Chem. Soc. 1998, 120, 3805.
33. Shaughnessy, K. H.; Waymouth, R. M. Organometallics 1998, 17, 5728.
34. Knight, K. S.; Wang, D.; Waymouth, R. M.; Ziller, J. J. Am. Chem. Soc. 1994, 116, 1845.
35. LaPointe, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906.
36. Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1995, 117, 1137.
37. Rix, F. C.; Brookhart, M.; White, P. S. J. Am. Chem. Soc. 1996, 118, 4746.
38. Goj, L. A.; Widenhoefer, R. A. J. Am. Chem. Soc. 2001, 123, 11290.
39. A portion of these results have been communicated: Perch, N. S.; Widenhoefer, R. A. Organometallics 2001, 20, 5251.
40. 1H NMR.
41. Benn, R.; Rufiñska, A. J. Organomet. Chem. 1982, 238, C27.
42. Albright, T. A.; Hoffmann, R.; Thibeault, J. C.; Thorn, D. L. J. Am. Chem. Soc. 1979, 101, 3801 and ref 23 therein.
43. We cannot rule out a structure for 5 in which the α -(triethylsilyl)methyl group and the terminus of the complexed olefin have a cis relationship. However, if this were the case, cis to trans isomerization must precede conversion of 5 to 6, and this isomerization must be fast relative to the conversion of 5 to 6 as the rate of conversion of 5 to 6 was independent of [NCAr].
44. Johnson, L. K.; Mecking, S.; Brookhart, M. J. Am. Chem. Soc. 1996, 118, 267.
45. Mecking, S.; Johnson, L. K.; Wang, L.; Brookhart, M. J. Am. Chem. Soc. 1998, 120, 888.
46. Johnson, L. K.; Killian, C. M.; Brookhart, M. J. Am. Chem. Soc. 1995, 117, 6414.
47. Rix, F. C.; Brookhart, M.; White, P. S. J. Am. Chem. Soc. 1996, 118, 2436.
48. t = 0.0196 M (95% conversion).27b
49. (b) Frost, A. A.; Pearson, R. G. Kinetics and Mechanism; Wiley: New York, 1961; p 16.
50. (a) Exner, O. in Correlation Analysis in Chemistry; Recent Advances; Chapman, N. B., Shorter, J., Eds.; Plenum: New York, 1978; pp 439-540.
51. (b) Matsui, K.; Hepler, Can. J. Chem. 1974, 52, 2906.
52. The principle source of error in our kinetic measurements was determination of catalyst concentration, which stemmed from the difficulty in accurately weighing 2b into the NMR tube. Efforts to improve the accuracy of these measurements by employing stock solutions of 2b were unsuccessful due to the short lifetime of 2b in solution at ambient temperature.
53. Temple, D. J.; Johnson, L. K.; Huff, R. L.; White, P. S.; Brookhart, M. J. Am. Chem. Soc. 2000, 122, 6686.
54. Shultz, L. H.; Temple, D. J.; Brookhart, M. J. Am. Chem. Soc. 2001, 123, 11539.
55. (a) Shultz, L. H.; Brookhart, M. Organometallics 2001, 20, 3975.
56. (b) Temple, D. J.; Brookhart, M. Organometallics 1998, 17, 2290.
57. Hauptman, E.; Sabo-Etienne, S.; White, P. S.; Brookhart, M.; Garner, J. M.; Fagan, P. J.; Calabrese, J. C. J. Am. Chem. Soc. 1994, 116, 8038.
58. Brookhart, M.; Volpe, A. F.; Lincoln, D. M.; Horvath, I. T.; Millar, J. M. J. Am. Chem. Soc. 1990, 112, 5634.
59. (a) Brookhart, M.; Lincoln, D. M.; Bennett, M. A.; Pelling, S. J. Am. Chem. Soc. 1990, 112, 2691.
60. (b) Brookhart, M.; Grant, B. E. J. Am. Chem. Soc. 1993, 115, 2151.
61. Perch, N. S.; Widenhoefer, R. A. Unpublished results.
62. Margl, P.; Ziegler, T. J. Am. Chem. Soc. 1996, 118, 7337.
63. (a) Shultz, C. S.; Ledford, J.; DeSimone, J. M.; Brookhart, M. J. Am. Chem. Soc. 2000, 122, 6351.
64. (b) Svejda, S. A.; Johnson, L. K.; Brookhart, M. J. Am. Chem. Soc. 1999, 121, 10634.
65. (c) Brookhart, M.; Lincoln, D. M. J. Am. Chem. Soc. 1988, 110, 8719.
66. (a) Brookhart, M.; Hauptman, E.; Lincoln, D. M. J. Am. Chem. Soc. 1992 114, 10394.
67. (b) Wang, L.; Flood, T. C. J. Am. Chem. Soc. 1992, 114, 3169
68. Lehmkuhl, H. Pure Appl. Chem. 1986, 58, 495 and references therein.
69. Lehmkuhl, H.; Naydowski, C.; Benn, R.; Rufiñska, A.; Schroth, G.; Mynott, R.; Krüger, C. Chem. Ber. 1983, 116, 2447.
70. Flood, T. C.; Statler, J. A. Organometallics 1984, 3, 1795.
71. Jun, C.-H. Organometallics 1996, 15, 895.
72. Coulson, D. R. J. Am. Chem. Soc. 1969, 91, 200.
73. (a) Casey, C. P.; Hallenbeck, S. L.; Pollock, D. W.; Landis, C. R. J. Am. Chem. Soc. 1995, 117, 9770.
74. (b) Casey, C. P.; Hallenbeck, S. L.; Wright, J. M.; Landis, C. R. J. Am. Chem. Soc. 1997, 119, 9681.
75. (a) Flood, T. C.; Bitler, S. P. J. Am. Chem. Soc. 1984, 106, 6076.
76. (b) Ermer, S. P.; Struck, G. E.; Bitler, S. P.; Richards, R.; Bau, R.; Flood, T. C. Organometallics 1993, 12, 2634.
77. 2 group in the transition state [for the β-migratory insertion of 13], especially the former, make the transition state potentially quite atypical."46b
78. -1 relative to the corresponding acyclic alkyl complex.
79. (a) Watson, P. L. J. Am. Chem. Soc. 1982, 104, 6472.
80. (b) Horton, A. D. Organometallics 1996, 15, 2675.
81. (c) Guo, Z.; Swenson, D. C.; Jordan, R. F. Organometallics 1994, 13, 1424.
82. (d) Hajela, S.; Bercaw, J. E.; Organometallics 1994, 13, 1147.
83. Wang, X.; Stankovich, S. Z.; Widenhoefer, R. A. Organometallics 2002, 21, 901.
84. -: Cámpora, J.; Gutiérrez-Puebla, E.; López, J. A.; Monge, A. ; Palma, P.; del Rio, D.; Carmona, E. Angew. Chem., Int. Ed. 2001, 40, 3641.
85. (a) Doherty, N. M.; Bercaw, J. E. J. Am. Chem. Soc. 1985, 107, 2670.
86. (b) Berger, B. J. Santarsiero, B. D.; Trimmer, M. S. Bercaw, J. E. J. Am. Chem. Soc. 1988, 110, 3134.
87. 2 was consistent with orientation of the olefin in or near the coordination plane, and for this reason, no significant olefin rotation or reorganization of the pentenyl chain was required for olefin β-migratory insertion?.46b
88. (a) Thorn, D. L.; Hoffmann, R. J. Am. Chem. Soc. 1978, 100, 2079.
89. (b) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry; University Science Books: Mill Valley, CA, 1987.
90. ‡ for the conversion of 5 to 6 relative to the conversion of 14 to 15 is due to migration of a Pd-secondary alkyl group in the case of 5 and a palladium-primary alkyl group in the case of 14.
91. 1H NMR analysis under these conditions.
92. Hay, P. J. J. Am. Chem. Soc. 1981, 103, 1390.
93. Svensson, M.; Matsubara, T.; Morokuma, K. Organometallics 1996, 15, 5568.
94. Alternatively, Pd-C bond cleavage could occur via an oxidative addition/reductive elimination sequence.
95. 3) generated in the catalytic silane competition experiments.
96. 3 formed (3,3-dimethylbutyl)triethylsilane to the exclusion of (3,3-dimethylbutyl)triphenylsilane,14 which indicates that olefin insertion/silylation of 4e is much faster than is silyl exchange. Because NCAr and an olefin of 1 are of comparable ligating ability with respect to cationic Pd(II) complexes,36 this result strongly suggests that 4b does not undergo silyl exchange prior to conversion to 5.
97. ‡ should be destabilized by the decreasing electron density and increasing steric bulk of the silane.
98. 1/2 = 22 min at -41 °C) ensures rapid activation of precatalyst 2b relative to catalyst turnover.
99. 3 corresponds to a macroscopic rate constant for the conversion of 6 to 4b for the specific case where [NCAr] = 42 mM.