Probing the C-H activation of linear and cyclic ethers at (PNP)Ir

Organometallics

Volumn 28, Issue 15, 2009, Pages 4560-4570

  Whited, Matthew T ^a   Zhu, Yanjun ^b,c   Timpa, Samuel D ^c   Chen, Chun Hsing ^c   Foxman, Bruce M ^c   Ozerov, Oleg V ^a,c   Grubbs, Robert H ^a  

^a California Institute of Technology   (United States)

^b TEXAS A AND M UNIVERSITY   (United States)

^c BRANDEIS UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACIDIC LIGAND; BUTYL METHYL ETHER; C-C BONDS; C-H ACTIVATION; CARBENE COMPLEXES; CARBENES; CYCLIC ETHER; DECARBONYLATIONS; DIETHYL ETHERS; ELECTRON DENSITIES; ELECTRON-RICH; METHYL ETHERS; OXIDATIVE ADDITIONS; REACTION PATHWAYS; TERT-AMYL METHYL ETHERS; TERT-BUTYL METHYL ETHERS; TETRAHYDROFURANS; VINYL ETHERS;

ACTIVATION ANALYSIS; DEHYDROGENATION; IRIDIUM; IRIDIUM COMPOUNDS; ORGANIC COMPOUNDS; PHOSPHORUS COMPOUNDS; SUBSTRATES;

ETHERS;

EID: 68149163436     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om900395f     Document Type: Article

References (83)

1. For leading references, see: (a) Bergman, R. G. Nature 2007, 446, 391.
2. (b) Amdtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154.
3. (c) Crabtree, R. H. Chem. Rev. 1985, 85, 245.
4. (d) Labinger, J. A.; Bercaw, J. E. Nature 2002, 417, 507.
5. (e) Activation and Functionalization of C-H Bonds; Goldberg, K. I., Goldman, A. S., Eds.; ACS Symposium Series 885; American Chemical Society: Washington, DC, 2004.
6. (f) Periana, R. A.; Bhalla, G.; Tenn, W. J.; Young, K. J. H.; Liu, X. Y.; Mironov, O.; Jones, C. J.; Ziatdinov, V. R. J. Mol. Catal. A: Chem. 2004, 220, 7.
7. (g) Dick, A. R.; Sanford, M. S. Tetrahedron 2006, 62, 2439.
8. (a) van der Boom, M. E.; Milstein, D. Chem. Rev. 2003, 103, 1759.
9. (b) Goldman, A. S.; Renkema, K. B.; Czerw, M.; Krogh-Jespersen, K. Alkane Transfer-Dehydrogenation Catalyzed by a Pincer-Ligated Iridium Complex. In Activation and Functionalization of C-H Bonds; Goldberg, K. I., Goldman, A. S., Eds.; ACS Symposium Series 885; American Chemical Society: Washington, DC, 2004; pp 198-215.
10. (a) Fan, L.; Foxman, B. M.; Ozerov, O. V. Organometallics 2004, 23, 326.
11. (b) Ozerov, O. V.; Guo, C.; Papkov, V. A.; Foxman, B. M. J. Am. Chem. Soc. 2004, 126, 4792.
12. (a) Fan, L.; Yang, L.; Guo, C.; Foxman, B. M.; Ozerov, O. V. Organometallics 2004, 23, 4778.
13. (b) Weng, W.; Guo, C.; Moura, C.; Yang, L.; Foxman, B. M.; Ozerov, O. V. Organometallics 2005, 24, 3487.
14. (c) Fan, L.; Parkin, S.; Ozerov, O. V. J. Am. Chem. Soc. 2005, 127, 16772.
15. (d) Gatard, S.; Guo, C.; Foxman, B. M.; Ozerov, O. V. Organometallics 2007, 26, 6066.
16. (e) Zhu, Y.; Fan, L.; Chen, C.-H.; Finnell, S. R.; Foxman, B. M.; Ozerov, O. V. Organometallics 2007, 26, 6701.
17. (a) Whited, M. T.; Grubbs, R. H. J. Am. Chem. Soc. 2008, 130, 5874.
18. (b) Romero, P. E.; Whited, M. T.; Grubbs, R. H. Organometallics 2008, 27, 3422.
19. (c) Whited, M. T.; Grubbs, R. H. Organometallics 2008, 27, 5737.
20. (d) Whited, M. T.; Grubbs, R. H. J. Am. Chem. Soc. 2008, 130, 16476.
21. (e) Whited, M. T.; Grubbs, R. H. Organometallics 2009, 28, 161.
22. (a) Boutry, O.; Gutiérrez, E.; Monge, A.; Nicasio, M. C.; Pérez, P. J.; Carmona, E. J. Am. Chem. Soc. 1992, 114, 7288.
23. (b) Luecke, H. F.; Amdtsen, B. A.; Burger, P.; Bergman, R. G. J. Am. Chem. Soc. 1996, 118, 2517.
24. (c) Holtcamp, M. W.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1997, 119, 848.
25. (d) Slugovc, C.; Mereiter, K.; Trofrmenko, S.; Carmona, E. Angew. Chem., Int. Ed. 2000, 39, 2158.
26. (e) Carmona, E.; Paneque, M.; Santos, L. L.; Salazar, V. Coord. Chem. Rev. 2005, 249, 1729.
27. (f) Lee, D.-H.; Chen, J.; Faller, J. W.; Crabtree, R. H. Chem. Commun. 2001, 213.
28. (g) Coalter, J. N.; Ferrando, G.; Caulton, K. G. New J. Chem. 2000, 24, 835.
29. (h) Ferrando-Miguel, G.; Coalter, J. N.; Gerard, H.; Huffman, J. C.; Eisenstein, O.; Caulton, K. G. New J. Chem. 2002, 26, 687.
30. Fan, L. Ph.D. Thesis, Brandeis University, 2006.
31. (a) Fryzuk, M. D.; Macneil, P. A.; Rettig, S. J. J. Am. Chem. Soc. 1985, 107, 6708.
32. (b) Fryzuk, M. D.; Gao, X.; Joshi, K.; Macneil, P. A. J. Am. Chem. Soc. 1993, 115, 10581.
33. Whited, M. T.; Grubbs, R. H. Acc. Chem. Res., in press.
34. (a) Parkin, G.; Burger, B. J.; Trimmer, M. S.; Asselt, A. V.; Bercaw, J. E. J. Mol. Catal. 1987, 41, 21.
35. (b) Schrock, R. R.; Seidel, S. W.; Mösch-Zanetti, N. C.; Shih, K.-Y.; O'Donoghue, M. B.; Davies, W M.; Reiff, W. M. J. Am. Chem. Soc. 1997, 119, 11876.
36. (a) Carmona, E.; Paneque, M.; Poveda, M. L. Dalton Trans. 2003, 4022.
37. (b) Paneque, M.; Pověda, M. L.; Santos, L. L.; Carmona, E.; Lledós, A.; Ujaque, G.; Mereiter, K. Angew. Chem., Int. Ed. 2004, 43, 3708.
38. Holtcamp, M. W.; Henling, L. M.; Day, M. W.; Labinger, J. A.; Bercaw, J. E. Inorg. Chim. Acta 1998, 270, 467.
39. For a discussion on the nature of these intermediates, see Section IV.
40. (a) Jones, W. D.; Hessel, E. T. J. Am. Chem. Soc. 1993, 115, 554.
41. (b) Periana, R. A.; Bergman, R. G. Organometallics 1984, 3, 508.
42. (a) Gupta, M.; Kaska, W. C.; Jensen, C. M. Chem. Commun. 1997, 461.
43. (b) Zhang, X.; Fried, A.; Knapp, S.; Goldman, A. S. Chem. Commun. 2003, 2060.
44. Brookes, N. J.; Whited, M. T.; Ariafard, A.; Stranger, R.; Grubbs, R. H.; Yates, B. F., manuscript in preparation.
45. An alternative possibility is that hydrogen is lost directly from an α-oxoalkyl hydride intermediate via 1,2-elimination, although the previous observation of cis-dihydrido aminocarbenes for the (PNP)Ir system (ref 5c) and computational studies on the MTBE reaction (ref 18) seem to discount this mechanism.
46. Brookes, N. J.; Ariafard, A.; Stranger, R.; Yates, B. F. J. Am. Chem. Soc. 2009, 131, 5800.
47. The short C28-O1 bond length (1.31 Å) suggests that an alternative explanation for an elongated C27-C28 bond, namely, polarization of the vinyl ether, may be operative. This type of distortion serves to increase the σ-donating ability of heteroatom-substituted olefin ligands while reducing their π-acidity. However, the relatively similar Ir1 -C27 and Ir1 - C28 bond lengths as well as the expected low electrophilicity of the (PNP)Ir fragment indicate that the contribution from this sort of polarization is minimal. For leading references on polarization of bound vinyl ethers, see: (a) Chang, T. C. T.; Foxman, B. M.; Rosenblum, M.; Stockman, C. J. Am. Chem. Soc. 1981, 103, 7361.
48. (b) Watson, L. A.; Franzman, B.; Bollinger, J. C.; Caulton, K. G. New J. Chem. 2003, 27, 1769.
49. See, for example: (a) Gagnon, M. K. J.; St. Germain, T. R.; Vogels, C. M.; McNamara, R. A.; Taylor, N. J.; Westcott, S. A. Aust. J. Chem. 2000, 53, 693.
50. (b) Alickmann, D.; Frohlich, R.; Maulitz, A. H.; Wurthwein, E.-U. Eur. J. Org. Chem. 2002, 1523.
51. Nilsson, P.; Larhed, M.; Hallberg, A. J. Am. Chem. Soc. 2001, 123, 8217.
52. 6 metal complexes, see: (a) Lam, W. H.; Shimada, S.; Batsanov, A. S.; Lin, Z.; Marder, T. B.; Cowan, J. A.; Howard, J. A. K.; Mason, S. A.; McIntyre, G. J. Organometallics 2003, 22, 4557.
53. (b) Rachidi, I. E.-I.; Eisenstein, O.; Jean, Y. New J. Chem. 1990, 14, 671.
54. (c) Riehl, J.-F.; Jean, Y.; Eisenstein, O.; Pelissier, M. Organometallics 1992, 11, 729.
55. (d) Olivan, M.; Eisenstein, O.; Caulton, K. G. Organometallics 1997, 16, 2227.
56. (a) Fryzuk, M. D.; MacNeil, P. A.; Ball, R. G. J. Am. Chem. Soc. 1986, 108, 6414.
57. (b) Fryzuk, M. D.; MacNeil, P. A.; Massey, R. L.; Ball, R. G. J. Organomet. Chem. 1989, 328, 231.
58. Kanzelberger, M.; Singh, B.; Czerw, M.; Krogh-Jesperson, K.; Goldman, A. S. J. Am. Chem. Soc. 2000, 122, 11017.
59. For leading references, see: Procelewska, J.; Zahl, A.; Liehr, G.; van Eldik, R.; Smythe, N. A.; Williams, B. S.; Goldberg, K. I. Inorg. Chem. 2005, 44, 7732.
60. (a) Gozin, M.; Weisman, A.; Ben-David, Y.; Milstein, D. Nature 1993, 364, 699.
61. (b) Liou, S.-Y.; Gozin, M.; Milstein, D. J. Am. Chem. Soc. 1995, 117, 9774.
62. (c) Rybtchinski, B.; Vigalok, A.; Ben-David, Y.; Milstein, D. J. Am. Chem. Soc. 1996, 118, 12406.
63. sp3 cleavage in a pincer-type ligand, see refs 3b and 4b.
64. For an unusual case of C-C cleavage by β-phenyl elimination that does not involve a preorganized system, see: Cámpora, J.; Gutiérrez-Puebla, E.; López, J. A.; Monge, A.; Palma, P.; del Río, D.; Carmona, E. Angew. Chem., Int. Ed. 2001, 40, 3641.
65. See, for example: (a) Alaimo, P. J.; Arndtsen, B. A.; Bergman, R. G. J. Am. Chem. Soc. 1997, 119, 5269.
66. (b) Alaimo, P. J.; Arndtsen, B. A.; Bergman, R. G. Organometallics 2000, 19, 2130.
67. (a) Ohno, K.; Tsuji, J. J. Am. Chem. Soc. 1968, 90, 99.
68. (b) Abu-Hasanayn, F.; Goldman, M. E.; Goldman, A. S. J. Am. Chem. Soc. 1992, 114, 2520.
69. (c) Beck, C. M.; Rathmill, S. E.; Park, Y. J.; Chen, J.; Crabtree, R. H.; Liable-Sands, L. M.; Rheingold, A. L. Organometallics 1999, 18, 5311.
70. (d) Fristrup, P.; Kreis, M.; Palmelund, A.; Norrby, P-O.; Madsen, R. J. Am. Chem. Soc. 2008, 130, 5206.
71. This step bears some resemblance to the β-hydrogen elimination and loss of olefin that occurs in transfer dehydrogenation schemes at pincer-supported iridium centers. For a discussion of the mechanism of these types of reactions, see: Renkema, K. B.; Kissin, Y. V.; Goldman, A. S. J. Am. Chem. Soc. 2003, 125, 7770.
72. Such a stereoselective 1,2-migration is similar to what we and others have previously observed in the decarbonylation of formaldehyde (ref 5b).
73. Baldwin, J. E. J. Chem. Soc., Chem. Commun. 1976, 734.
74. Van der Sluys, L. S.; Kubas, G. J.; Caulton, K. G. Organometallics 1991, 10, 1033.
75. Klei, S. R.; Golden, J. T.; Tilley, T. D.; Bergman, R. G. J. Am. Chem. Soc. 2002, 124, 2092.
76. Zhang, X.; Emge, T. J.; Ghosh, R.; Goldman, A. S. J. Am. Chem. Soc. 2005, 127, 8250.
77. For leading references on C-C activation, see: Rybtchinski, B.; Milstein, D. Angew. Chem., Int. Ed. 1999, 38, 870.
78. Walker, J. F.; Chadwick, A. F. Ind. Eng. Chem. 1947, 39, 974.
79. Ozerov, O. V.; Pink, M.; Watson, L. A.; Caulton, K. G. J. Am. Chem. Soc. 2004, 126, 2105.
80. Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics 1996, 15, 1518.
81. Apex2, Version 2 User Manual, M86-E01078; Bruker Analytical X-ray Systems: Madison, WI, 2006.
82. Altomare, A.; Cascarano, G.; Giacovazzo, G.; Guagliardi, A.; Burla, M. C.; Polidori, G.; Camalli, M. J. Appl. Crystallogr. 1994, 27, 435.
83. Betteridge, P. W.; Carruthers, J. R.; Cooper, R. I.; Prout, K.; Watkin, D. J. J. Appl. Crystallogr. 2003, 36, 1487.