Understanding structural isomerization during ruthenium-catalyzed olefin metathesis: A deuterium labeling study

Organometallics

Volumn 25, Issue 26, 2006, Pages 6074-6086

  Courchay, Florence C ^a   Sworen, John C ^a   Ghiviriga, Ion ^a   Abboud, Khalil A ^a   Wagener, Kenneth B ^a  

^a UNIVERSITY OF FLORIDA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC RINGS; BENZYLIDENES; METATHESIS; RUTHENIUM DIHYDRIDES;

CATALYSIS; DECOMPOSITION; ETHERS; ISOMERIZATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; RUTHENIUM; SYNTHESIS (CHEMICAL);

OLEFINS;

EID: 33846384067     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om0509894     Document Type: Article

References (103)

1. (a) Schwab, P.; Grubbs, R. H.; Ziller, J. J. Am. Chem. Soc. 1996,118, 100-110.
2. (b) Dias, E. L.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997,119, 3887-3897.
3. (c) Ulman, M.; Grubbs, R. H. Organometallics 1998, 17, 2484-2489.
4. (d) Ulman, M.; Grubbs, R. H. J. Org. Chem. 1999,64, 7202-7207.
5. For relevant reviews, see: (a) Handbook of Metathesis; Grubbs, R. H., Ed.; Wiley-VCH: Weinheim, Germany, 2003.
6. (b) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001,34, 18-29.
7. (c) Fürstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043.
8. (d) Grubbs, R. H.; Chang, S. Tetrahedron 1998,54. 4413-4450.
9. (e) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. 1997,36, 2036-2056.
10. (f) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388.
11. (g) Frenzel, U.; Nuyken, O. J. Polym. Sci.: Chem. 2002,40, 2895-2916.
12. (a) Scholl, M.; Ding, S.; Lee, C.; Grubbs, R. H. Org. Lett. 1999,1, 953-956.
13. (b) Sanford, M. S.; Ulman, M.; Grubbs, R. H. J. Am. Chem. Soc. 2001,123, 749-750.
14. (c) Sanford, M. S.: Love, J. A.; Grubbs, R. H. J. Am. Chem. Soc. 2001,123, 6543-6554.
15. (a) Scholl, M.; Trnka, T. M.; Morgan, J. P.; Grubbs, R. H. Tetrahedron Lett. 1999,40, 2247-2250.
16. (b) Weskamp, T.; Kohl, F. J.; Herrmann, W. A. J. Organomet. Chem. 1999,582, 362-365.
17. (c) Ackermann, L.; Fürstner, A.; Westcamp, T.; Kohl, F. J.; Herrmann, W. A. Tetrahedron Lett. 1999,40, 4787-4790.
18. (d) Huang, J.; Stephens, E. D.; Nolan, S. P.; Pedersen, J. L. J. Am. Chem. Soc. 1999,121, 2674-2678.
19. (a) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J.; Hoveyda, A. H. J. Am. Chem. Soc. 1999,121, 791-799.
20. (b) Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000,122, 8168-8179.
21. (c) For a review on Ru-bearing bidentate carbenes: Hoveyda, A. H.; Gillingham, D. G.; Van Veldhuizen, J. J.; Kataoka, O.; Garber, S. B.; Kingsbury, J. S.; Harrity, J. P. A. Org. Biomol. Chem. 2004,2, 8-23.
22. (a) Love, J. A.; Morgan, J. P.; Trnka, T. M.; Grubbs, R. H. Angew. Chem., Int. Ed. 2002,41, 4035-4037.
23. (b) Love, J. A.; Sanford, M. S.; Day, M. W.; Grubbs, R. H. J. Am. Chem. Soc. 2003,125, 10103-10109.
24. (a) For a review on non-metathetic behavior of Ru carbenes, see: Alcaide, B.; Almendros, P. Chem. Eur. J. 2003,9, 1258-1262.
25. (b) Schmidt, B.; Pohler, M.; Costisella, B. J. Org. Chem. 2004,69, 1421-1424.
26. (c) Faulkner, J.; Edlin, C. D.; Fengas, D.; Preece, I.; Quayle, P.; Richards, S. N. Tetrahedron Lett. 2005,46, 2381-2385.
27. (d) Edlin, C. D.; Faulkner, J.; Fengas, D.; Knight, C. K.; Parker, J.; Preece, I.; Quayle, P.; Richards, S. N. Synlett 2005,4, 572-577.
28. (e) Hoye, T. R.; Zhao, H. Org. Lett. 1999,1, 169-171.
29. (f) Gurjar, M. K.; Yakambram, P. Tetrahedron Lett. 2001,42, 3633-3636.
30. For a short review on the isomerization behavior of ruthenium carbenes, see: Schmidt, B. Eur. J. Org. Chem. 2004,9, 1865-1880.
31. (a) Miller, S. J.; Blackwell, H. E.; Grubbs, R. H. J. Am. Chem. Soc. 1996,118, 9606-9614.
32. (b) Maynard, H. D.; Grubbs, R. H. Tetrahedron Lett. 1999,40, 4137-4140.
33. (c) Bourgeois, D.; Pancrazi, A.; Ricard, L.; Prunet, J. Angew. Chem. 2000,112, 742-744;
34. Angew. Chem., Int. Ed. 2000, 39, 725-728.
35. (d) Edwards, S. D.; Lewis, T.; Taylor, R. J. K. Tetrahedron Lett. 1999,40, 4267-4270.
36. (e) Schmidt, B.; Wildemann, H. J. Org. Chem. 2000, 65, 5817-5822.
37. (a) Fürstner, A.; Thiel, O. R.; Ackermann, L.; Schanz, H.-J.; Nolan, S. P. J. Org. Chem. 2000,65, 2204-2207.
38. (b) Cadot, C.; Dalko, P. I.; Cossy, J. Tetrahedron Lett. 2002,43, 1839-1841.
39. (c) Sutton, A. E.; Seigal, B. A.; Finnegan, D. F.; Snapper, M. L. J. Am. Chem. Soc. 2002,124, 13390-13391.
40. (d) Bourgeois, D.; Pancrazi, A.; Nolan, S. P.; Prunet, J. J. Organomet. Chem. 2002,643-644, 247-252.
41. (e) Sworen, J. C.; Pawlow, J. H.; Case, W.; Lever, J.; Wagener, K. B. J. Mol. Catal. 2002,194, 69-78.
42. (a) Lehman, S. E.; Schwendeman, J. E.; O'Donnell, P. M.; Wagener, K. B. Inorg. Chim. Acta 2002,345, 190-198.
43. (b) Courchay, F. C.; Sworen, J. C.: Wagener, K. B. Macromolecules 2003,36, 8231-8239.
44. Crabtree, R. H. The Organometallic Chemistry of the Transition Metals,2nd ed.; Wiley: New York, 1994.
45. (a) Hendrix, W. T.; Cowherd, F. G.; von Rosenberg, J. L. Chem. Commun. 1968, 97-99.
46. (b) Bergens, S. H.; Bosnien, B. J. Am. Chem. Soc. 1991,113, 958-967.
47. (c) McGrath, D. V.; Grubbs, R. H. Organometallics 1994,13, 224-235.
48. (d) Baudry, D.; Ephritikhine, M.; Felkin, H. J. Chem. Soc., Chem. Commun. 1978, 694-695.
49. (e) Clark, H. C.; Kurosawa, H. Inorg. Chem. 1973,12, 1566-1569.
50. (f) Casey, C. P.; Cyr, C. R. J. Am. Chem. Soc. 1973,95, 2248-2253.
51. For relevant reviews on the reactivity of ruthenium hydride complexes, see: (a) Naota, T.; Takaya, H.; Murahashi, S. Chem. Rev. 1998,98, 2599-2660.
52. (b) Trost, B. M.; Toste, F. D.; Pinkerton, A. B. Chem. Rev. 2001,101, 2067-2096.
53. (a) Drouin, S. D.; Yap, G. P. A.; Fogg, D. E. Inorg. Chem. 2000,39, 5412-5414.
54. (b) Fogg, D. E.; Drouin, S. D.; Zamanian, F. U.S. Pat. Appl. 60/ 192394, priority date March 26, 2000.
55. (c) Beatty, R. P.; Paciello, R. A. U.S. Patent 5,554,778, 1996.
56. (a) Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995,117, 5503-5511.
57. (b) Louie, J.; Grubbs, R. H. Organometallics 2002, 21, 2153-2164.
58. (a) Dinger, M. B.; Mol, J. C. Organometallics 2003, 22, 1089-1095.
59. (b) Dinger, M. B.; Mol, J. C. Eur. J. Inorg. Chem. 2003, 2827-2833.
60. (c) Banti, D.; Mol, J. C. J. Organomet. Chem. 2004,689, 3113-3116.
61. (d) Trnka, T. M.; Morgan, J. P.; Sanford, M. S.; Wilhem, T. E.; Scholl, M.; Choi, T.-L.; Ding, S.; Day, M. D.; Grubbs, R. H. J. Am. Chem. Soc. 2003,125, 2546-2558.
62. (a) Yi, C. S.; Lee, D. W. Organometallics 1999,18, 5152-5156.
63. (b) Yi, C. S.; Lee, D. W.; He, Z.; Rheingold, A. L.; Lam, K.-C.; Concolino, T. E. Organometallics 2000,19, 2909-2915.
64. (c) Lee, H. M.; Smith, D. C.; Zhengjie, H.; Stevens, E. D.; Yi, C. S.; Nolan, S. P. Organometallics 2001,20, 794-797.
65. (d) Dharmasena, U. L.; Foucault, H. M.; dos Santos, E. N.; Fogg, D. E.; Nolan, S. P. Organometallics 2005,24, 1056-1058.
66. Esteruelas, M. A.; Werner, H. J. Organomet. Chem. 1986,303, 221-231.
67. Hong, S. H.; Day, M. W.; Grubbs, R. H. J. Am. Chem. Soc. 2004,126, 7414-7415.
68. Jazzar, R. F. R.; Macgregor, S. A.; Mahon, M. F.; Richards, S. P.; Whittlesey, M. K. J. Am. Chem. Soc. 2002,124, 4944-4945.
69. (a) Wagener, K. B.; Valenti, D. J.; Hahn, S. F. Macromolecules 1997,30, 6688-6690.
70. (b) Smith, J. A.; Brzezinska, K. R.; Valenti, D. J.; Wagener, K. B. Macromolecules 2000,33, 3781-3794.
71. (c) Sworen, J. C.; Smith, J. A.; Berg, J. M.; Wagener, K. W. J. Am. Chem. Soc. 2004,126, 11238-11246.
72. Courchay, F. C. Ph.D. Dissertation, University of Florida, 2005.
73. Werner, H.; Grunwald, C.; Stuer, W.; Wolf, J. Organometallics 2003,22, 1558-1560.
74. The details of NMR and NOE experiments are available in the Supporting Information.
75. 3 methyl ether.
76. Cramer, R. J. Am. Chem. Soc. 1966,88, 2272-2282.
77. Krompiec, S.; Antoszczyszyn, M.; Urbala, M.; Bieg, T. Pol. J. Chem. 2000,74, 737-741.
78. Traces of deuterium incorporation at the olefinic bond of the starting material were also observed, suggesting the presence of a metal hydride at this early stage of the reaction.
79. 2 methyl ether.
80. Crystals suitable for X-ray structure determination were obtained from slow diffusion of pentane into a saturated solution of 8 in benzene at room temperature.
81. Crystal data for compound 8 are available as Supporting Information.
82. The decomposition is indicated by the steady disappearance of the carbene signal at δ 19.63 ppm.
83. 1H NMR by integration of the internal olefin peak at δ 5.40 ppm.
84. 1H NMR, these conditions led to the complete transformation of benzylidene 8 into the methylidene, which decomposed rapidly, as indicated by the disappearance of the methylidene signal at 18.40 ppm.
85. The deuterium content observed here is much superior to the levels naturally found in benzene.
86. Giunta, D.; Hölsher, M.; Lehmann, C. W.; Mynott, R.; Wirtz, C.; Leitner, W. Adv. Synth. Catal. 2003,345, 1139-1145.
87. (a) Burtling, S.; Mahon, M. F.; Paine, B. M.; Whittlesey, M. K.; Williams, J. M. J. Organometallics 2004,23, 4537-4539.
88. (b) Abdur-Rashid, K.; Fedorkiw, T.; Lough, A. J.; Morris, R. H. Organometallics 2004,23, 86-94.
89. van Rensburg, W. J.; Steynberg, P. J.; Meyer, W. H.; Kirk, M. M.; Forman, G. S. J. Am. Chem. Soc. 2004,126, 14332-14333.
90. Due to the large excess of allyl methyl ether, we suppose that at early reaction times the molecules are only monodeuterated, since they are not likely to react again with another ruthenium deuteride.
91. Ulman, M.; Grubbs, R. H. Organometallics 1998,17, 2484-2489.
92. (a) Owen, M. A.; Pye, P. L.; Piggott, B.;Capparelli, M. V. J. Organomet. Chem. 1992,434, 351-362.
93. (b) Hitchcock, P. B.; Lappert, M. F.; Pye, P. L.; Thomas, S. J. Chem. Soc., Dalton Trans. 1979,88, 1929-1942.
94. Rankin, M. A.; McDonald, R.; Ferguson, M. J.; Stradiotto, M. Angew. Chem., Int. Ed. 2005,44, 3603-3606.
95. Hansen, S. M.; Rominger, F.; Metz, M.; Hofmann, P. Chem. Eur. J. 1999,5, 557-566.
96. A recent paper shows the use of benzoquinone to prevent olefin isomerization during metathesis reactions: Hong, S. H.; Sanders, D. P.; Lee, C. W.; Grubbs, R. H. J. Am. Chem. Soc. 2005,127, 17160-17161.
97. Scholl, M.; Ding, S.; Lee, C.; Grubbs, R. H. Org. Lett. 1999,1, 953-956.
98. McGrath, D. V.; Grubbs, R. H. Organometallics 1994, 13, 224-235.
99. Nishiyama, K.; Tanaka, N. J. Chem. Soc., Chem. Commun. 1983,22, 1322-1323.
100. SHELXTL6: Bruker-AXS, Madison, WI, 2000.
101. Fieser, L. F.; Fieser, M. Reagents for Organic Synthesis; Wiley: New York, 1967; Vol. 1, pp 581-585.
102. Arduengo, A. J., III; Krafczyk, R.; Schmutzler, R.; Craig, H. A.; Goerlich, J. R.; Marshall, W. J.; Unverzagt, M. Tetrahedron 1999,55, 14523-14534.
103. Trnka, T. M.; Morgan, J. P.; Sanford, M. S.; Wilhem, T. E.; Scholl, M.; Choi, T.-L.; Ding, S.; Day, M. D.; Grubbs, R. H. J. Am. Chem. Soc. 2003,125, 2546-2558.