Ruthenium alkoxycarbene complexes from an acetal function by C-O bond cleavage and alcohol elimination

Organometallics

Volumn 15, Issue 13, 1996, Pages 2860-2862

  Grotjahn, D B ^a   Lo, H C ^a  

^a ARIZONA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000161522     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om9603171     Document Type: Article

References (46)

1. (a) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587-608.
2. (b) Transition Metal Carbene Complexes; Seyferth, D., Ed.; VCH: Weinheim, Germany, 1983.
3. (c) Wulff, W. D. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 5, pp 1065-1113.
4. (d) Wulff, W. D. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1989; Vol. 1, pp 209-393.
5. Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503-5511 and references therein.
6. Imwinkelried, R.; Hegedus, L. S. Organometallics 1988, 7, 702-706. Dvorák, D. Organometallics 1995, 14, 570-573.
7. Imwinkelried, R.; Hegedus, L. S. Organometallics 1988, 7, 702-706. Dvorák, D. Organometallics 1995, 14, 570-573.
8. Semmelhack, M. F.; Ho, S.; Cohen, D.; Steigerwald, M.; Lee, M. C.; Lee, G.; Gilbert, A. M.; Wulff, W. D.; Ball, R. G. J. Am. Chem. Soc. 1994, 116, 7108-7122.
9. (a) Seitz, W. J.; Saha, A. K.; Hossain, M. M. Organometallics 1993, 12, 2604-2608.
10. (b) Müller, P.; Baud, C.; Ené, D.; Motallebi, S.; Doyle, M. P.; Brandes, B. D.; Dyatkin, A. B.; See, M. M. Helv. Chim. Acta 1995, 78, 459-470 and references therein.
11. Schmitz, E.; Eichhorn, I. Acetals and Hemiacetals. In The Chemistry of the Ether Linkage; Patai, S., Ed.; Interscience: London, 1967; Chapter 7, pp 310-351.
12. For organic routes to free alkoxycarbenes, see: Heydt, H.; Regitz, M. Hydroxy-, Organooxy-, Silyloxy-carbene. In Houben-Weyl Methoden der Organischen Chemie; Thieme: Stuttgart, Germany, 1989; Band E19b, pp 1628-1682.
13. (a) Boutry, O.; Gutiérrez, E.; Monge, A.; Nicasio, M. C.; Pérez, P. J.; Carmona, E. J. Am. Chem. Soc. 1992,114, 7288-7290. Gutiérrez, E.; Monge, A.; Nicasio, M. C.; Poveda, M. L.; Carmona, E. J. Am. Chem. Soc. 1994, 116, 791-792.
14. (a) Boutry, O.; Gutiérrez, E.; Monge, A.; Nicasio, M. C.; Pérez, P. J.; Carmona, E. J. Am. Chem. Soc. 1992,114, 7288-7290. Gutiérrez, E.; Monge, A.; Nicasio, M. C.; Poveda, M. L.; Carmona, E. J. Am. Chem. Soc. 1994, 116, 791-792.
15. (b) Luecke, H. F.; Arndtsen, B. A.; Burger, P.; Bergman, R. G. J. Am. Chem. Soc. 1996, 118, 2517-2518.
16. (c) Werner, H.; Weber, B.; Nürnberg, O.; Wolf, J. Angew. Chem., Int. Ed. Engl. 1992, 31, 1025-1027.
17. (d) Li, Z.-W.; Taube, H. J. Am. Chem. Soc. 1994, 116, 11584-11585.
18. (e) Aminals to aminocarbene ligands on clusters: Adams, R. D. Chem. Rev. 1989, 89, 1703-1712.
19. Review: Bruce, M. I.; Swincer, A. G. Adv. Organomet. Chem. 1983, 22, 59-128, especially pp 69-73.
20. Hoots, J. E.; Rauchfuss, T. B.; Wroblenski, D. A. Inorg. Synth. 1982, 21, 175-179.
21. (a) Gill, T. P.; Mann, K. R. Organometallics 1982, 1, 485-488.
22. 11c
23. (c) Rapaport, I.; Helm, L.; Merbach, A. E.; Bernhard, P.; Ludi, A. Inorg. Chem. 1988, 27, 873-879.
24. 1H) NMR, IR and (with the exception of 3) elemental analysis.
25. 3) δ 46.44.
26. 3) δ 76.97; correct analyses for C, H, N, and S.
27. Leading references: Gamasa, M. P.; Gimeno, J.; Martín-Vaca, B. M.; Borge, J.; García-Granda, S.; Perez-Carreño, E. Organometallics 1994, 13, 4045-4057. Pilette, D.; Ouzzine, K.; Le Bozec, H.; Dixneuf, P. H.; Rickard, C. E. F.; Roper, W. R. Organometallics 1992, 11, 809-817.
28. Leading references: Gamasa, M. P.; Gimeno, J.; Martín-Vaca, B. M.; Borge, J.; García-Granda, S.; Perez-Carreño, E. Organometallics 1994, 13, 4045-4057. Pilette, D.; Ouzzine, K.; Le Bozec, H.; Dixneuf, P. H.; Rickard, C. E. F.; Roper, W. R. Organometallics 1992, 11, 809-817.
29. Weak IR absorption of coordinated nitriles: Rouschias, G.; Wilkinson, G. J. Chem. Soc. A 1967, 993-1000.
30. C-H activations of alkanes and arenes: Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91-100. Crabtree, R. H.; Hamilton, D. G. Adv. Organomet. Chem. 1988, 28, 299-338. Ryabov, A. D. Chem. Rev. 1990, 90, 403-424.
31. C-H activations of alkanes and arenes: Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91-100. Crabtree, R. H.; Hamilton, D. G. Adv. Organomet. Chem. 1988, 28, 299-338. Ryabov, A. D. Chem. Rev. 1990, 90, 403-424.
32. C-H activations of alkanes and arenes: Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91-100. Crabtree, R. H.; Hamilton, D. G. Adv. Organomet. Chem. 1988, 28, 299-338. Ryabov, A. D. Chem. Rev. 1990, 90, 403-424.
33. Treatment of α-alkoxyalkyl complexes with acid or other electrophiles can lead to carbene complexes with loss of the alkoxy group: Jolly, P. W.; Pettit, R. J. Am. Chem. Soc. 1966, 88, 5044-5055. Review: Brookhart, M.; Studabaker, W. B. Chem. Rev. 1987, 87, 411-432.
34. Treatment of α-alkoxyalkyl complexes with acid or other electrophiles can lead to carbene complexes with loss of the alkoxy group: Jolly, P. W.; Pettit, R. J. Am. Chem. Soc. 1966, 88, 5044-5055. Review: Brookhart, M.; Studabaker, W. B. Chem. Rev. 1987, 87, 411-432.
35. This is apparently unknown for acetals: Yamamoto, A. Adv. Organomet. Chem. 1992, 34, 111-147.
36. Deprotonation of dialkoxycarbonium ions by hindered amines: Olofson, R. A.; Walinsky, S. W.; Marino, J. P.; Jernow, J. L. J. Am. Chem. Soc. 1968, 90, 6554-6555. See also ref 7.
37. 3-SiOTf (ca. 0.1 equiv) to reactions of 3a led to faster but considerably messier reactions, and the non-coordinating base 2,4,6-tris(tert-butyl)-pyridine (1 equiv) had little effect on the rate. The negligible influence of added base shows that traces of acidic impurities are not responsible for the reactions described.
38. Luginbühl, W.; Zbinden, P.; Pittet, P. A.; Armbruster, T.; Bürgi, H.-B.; Merbach, A. E.; Ludi, A. Inorg. Chem. 1991, 30, 2350-2355.
39. 3CN on heating at 60 °C for several days.
40. Low isotope effects in C-H bond activation processes have been attributed to nonlinear hydrogen transfer or an early transition state; see ref 17.
41. Shiner, V. J., Jr. In Isotope Effects in Chemical Reactions; Collins, C. J., Bowman, N. S., Eds.; Litton Educational Publishing: New York, 1970; pp 135-136. See also: Reaction Rates of Isotopic Molecules; Melander, L., Saunders, W. H., Jr., Eds.; Wiley: New York, 1980; pp 172-174.
42. Shiner, V. J., Jr. In Isotope Effects in Chemical Reactions; Collins, C. J., Bowman, N. S., Eds.; Litton Educational Publishing: New York, 1970; pp 135-136. See also: Reaction Rates of Isotopic Molecules; Melander, L., Saunders, W. H., Jr., Eds.; Wiley: New York, 1980; pp 172-174.
43. Reichardt, C. Solvents and Solvent Effects in Organic Chemistry; VCH: Weinheim, Germany, 1988.
44. 3) (M = Rh, Ir) for primary C-H bonds of propane and hexane are the same within a factor of 2: Jones, W. D. In Activation and Functionalization of Alkanes; Hill, C. L., Ed.; Wiley: New York, 1989.
45. 3).
46. Davison, A.; Reger, D. L. J. Am. Chem. Soc. 1972, 94, 9237-9238.