First stepwise Dotz reaction: Isolation and characterization of a chelated metallatriene intermediate. Influence of its pattern of substitution in product partition

Journal of the American Chemical Society

Volumn 122, Issue 7, 2000, Pages 1314-1324

  Barluenga, José ^a   Aznar, Fernando ^a   Gutiérrez, Ignacio ^a   Martín, Alfredo ^a,b   García Granda, Santiago ^a   Amparo Llorca Baragano M ^a  

^a UNIVERSITY OF OVIEDO   (Spain)

^b ELI LILLY AND COMPANY   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

CARBENE;

ARTICLE; CHEMICAL STRUCTURE; COMPLEX FORMATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 0033998175     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991865j     Document Type: Article

References (73)

1. For reviews on the synthetic applications of Fischer carbene complexes, see: (a) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (b) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 469-547. (c) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 549-576. (d) Doyle, M. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 387-420. (e) Harvey, D. F.; Sigano, D. M. Chem. Rev. 1996, 96, 271.
2. For reviews on the synthetic applications of Fischer carbene complexes, see: (a) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (b) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 469-547. (c) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 549-576. (d) Doyle, M. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 387-420. (e) Harvey, D. F.; Sigano, D. M. Chem. Rev. 1996, 96, 271.
3. For reviews on the synthetic applications of Fischer carbene complexes, see: (a) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (b) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 469-547. (c) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 549-576. (d) Doyle, M. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 387-420. (e) Harvey, D. F.; Sigano, D. M. Chem. Rev. 1996, 96, 271.
4. For reviews on the synthetic applications of Fischer carbene complexes, see: (a) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (b) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 469-547. (c) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 549-576. (d) Doyle, M. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 387-420. (e) Harvey, D. F.; Sigano, D. M. Chem. Rev. 1996, 96, 271.
5. For reviews on the synthetic applications of Fischer carbene complexes, see: (a) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (b) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 469-547. (c) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 549-576. (d) Doyle, M. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 387-420. (e) Harvey, D. F.; Sigano, D. M. Chem. Rev. 1996, 96, 271.
6. For discussions of, and recent citations to mechanistic issues, see: (a) Waters, M. L.; Brandvold, T. A.; Isaacs, L.; Wulff, W. D.; Rheingold, A. L. Organometallics 1998, 17, 4298. (b) Hsung, R. P.; Quinn, J. F.; Weisemberg, B. A.; Wulff, W. D.; Yap, G. P. A.; Rheingold, A. L. Chem. Commun. 1997, 615. (c) Gross, M. F.; Finn, M. G. J. Am. Chem. Soc. 1994, 116, 10921. (d) Wulff, W. D.; Bax, B. M.; Brandvold, T. A.; Chan, K. S.; Gilbert, A. M.; Hsung, R. P.; Mitchell, J.; Clardy, J. Organometallics 1994, 13, 102. (e) Bos, M. E.; Wulff, W. D.; Miller, R. A.; Chamberlin, S.; Brandvold, T. A. J. Am. Chem. Soc. 1991, 113, 9293.
7. For discussions of, and recent citations to mechanistic issues, see: (a) Waters, M. L.; Brandvold, T. A.; Isaacs, L.; Wulff, W. D.; Rheingold, A. L. Organometallics 1998, 17, 4298. (b) Hsung, R. P.; Quinn, J. F.; Weisemberg, B. A.; Wulff, W. D.; Yap, G. P. A.; Rheingold, A. L. Chem. Commun. 1997, 615. (c) Gross, M. F.; Finn, M. G. J. Am. Chem. Soc. 1994, 116, 10921. (d) Wulff, W. D.; Bax, B. M.; Brandvold, T. A.; Chan, K. S.; Gilbert, A. M.; Hsung, R. P.; Mitchell, J.; Clardy, J. Organometallics 1994, 13, 102. (e) Bos, M. E.; Wulff, W. D.; Miller, R. A.; Chamberlin, S.; Brandvold, T. A. J. Am. Chem. Soc. 1991, 113, 9293.
8. For discussions of, and recent citations to mechanistic issues, see: (a) Waters, M. L.; Brandvold, T. A.; Isaacs, L.; Wulff, W. D.; Rheingold, A. L. Organometallics 1998, 17, 4298. (b) Hsung, R. P.; Quinn, J. F.; Weisemberg, B. A.; Wulff, W. D.; Yap, G. P. A.; Rheingold, A. L. Chem. Commun. 1997, 615. (c) Gross, M. F.; Finn, M. G. J. Am. Chem. Soc. 1994, 116, 10921. (d) Wulff, W. D.; Bax, B. M.; Brandvold, T. A.; Chan, K. S.; Gilbert, A. M.; Hsung, R. P.; Mitchell, J.; Clardy, J. Organometallics 1994, 13, 102. (e) Bos, M. E.; Wulff, W. D.; Miller, R. A.; Chamberlin, S.; Brandvold, T. A. J. Am. Chem. Soc. 1991, 113, 9293.
9. For discussions of, and recent citations to mechanistic issues, see: (a) Waters, M. L.; Brandvold, T. A.; Isaacs, L.; Wulff, W. D.; Rheingold, A. L. Organometallics 1998, 17, 4298. (b) Hsung, R. P.; Quinn, J. F.; Weisemberg, B. A.; Wulff, W. D.; Yap, G. P. A.; Rheingold, A. L. Chem. Commun. 1997, 615. (c) Gross, M. F.; Finn, M. G. J. Am. Chem. Soc. 1994, 116, 10921. (d) Wulff, W. D.; Bax, B. M.; Brandvold, T. A.; Chan, K. S.; Gilbert, A. M.; Hsung, R. P.; Mitchell, J.; Clardy, J. Organometallics 1994, 13, 102. (e) Bos, M. E.; Wulff, W. D.; Miller, R. A.; Chamberlin, S.; Brandvold, T. A. J. Am. Chem. Soc. 1991, 113, 9293.
10. For discussions of, and recent citations to mechanistic issues, see: (a) Waters, M. L.; Brandvold, T. A.; Isaacs, L.; Wulff, W. D.; Rheingold, A. L. Organometallics 1998, 17, 4298. (b) Hsung, R. P.; Quinn, J. F.; Weisemberg, B. A.; Wulff, W. D.; Yap, G. P. A.; Rheingold, A. L. Chem. Commun. 1997, 615. (c) Gross, M. F.; Finn, M. G. J. Am. Chem. Soc. 1994, 116, 10921. (d) Wulff, W. D.; Bax, B. M.; Brandvold, T. A.; Chan, K. S.; Gilbert, A. M.; Hsung, R. P.; Mitchell, J.; Clardy, J. Organometallics 1994, 13, 102. (e) Bos, M. E.; Wulff, W. D.; Miller, R. A.; Chamberlin, S.; Brandvold, T. A. J. Am. Chem. Soc. 1991, 113, 9293.
11. Fischer, H.; Mühlemeier, J.; Märkl, R.; Dötz, K. H. Chem. Ber. 1982, 115, 1355.
12. (a) Dötz, K. H.; Dietz, R. Chem. Ber. 1978, 111, 2517.
13. (b) Dötz, K. H.; Pruskil, I. Chem. Ber. 1980, 113, 2876.
14. (c) Wulff, W. D.; Tang, P. C.; McCallum, J. S. J. Am. Chem. Soc. 1981, 103, 7677.
15. (d) Dötz, K. H.; Mühlemeier, J.; Schubert, U.; Orama, O. J. Organomet. Chem. 1983, 247, 187.
16. (e) Wulff, W. D.; Chang, K. S.; Tang, P. C. J. Org. Chem. 1984, 49, 2293.
17. (f) Yamashita, A.; Toy, A. Tetrahedron Lett. 1986, 27, 3471.
18. It has also been proposed for the formation of phenol (naphthol) IX a manifold involving CO insertion in complex V followed by reductive elimination and tautomerization: Casey, C. P. In Reactive Intermediates; Jones, M., Jr., Moss, R. A., Eds.; Wiley: New York, 1981; Vol. 2, p 155.
19. McCallum, J. S.; Kunng, F. A.; Gilbertson, S. R.; Wulff, W. D. Organometallics 1988, 7, 2346.
20. (a) Dötz, K. H.; Schäfer, T.; Kroll, F.; Harms, K. Angew. Chem., Int. Ed. Engl. 1992, 31, 1236.
21. (b) Hohmann, F.; Siemoneit, S.; Nieger, M.; Kotila, S.; Dötz, K. H. Chem. Eur. J. 1997, 3, 853.
22. Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1979, 18, 954.
23. (a) Anderson, B. A.; Wulff, W. D.; Rheingold, A. L. J. Am. Chem. Soc. 1990, 112, 8615.
24. (b) Chelain, E.; Goumont, R.; Hamon, L.; Parlier, A.; Rudler, M.; Rudler, H.; Daran, J. C.; Vaissermann, J. J. Am. Chem. Soc. 1992, 114, 8088.
25. Tang, P. C.; Wulff, W. D. J. Am. Chem. Soc. 1984, 106, 1132.
26. Gleichmann, M. M.; Dötz, K. H.; Hess, B. A. J. Am. Chem. Soc. 1996, 118, 10551.
27. (a) Hoffmann, P.; Hämmerle, M. Angew. Chem., Int. Ed. Engl. 1989, 28, 908.
28. (b) Hoffmann, P.; Hämmerle, M. Unfried, G. New J. Chem. 1991, 15, 769.
29. (a) Torrent, M.; Duran, M.; Solá, M. Organometallics 1998, 17, 1492.
30. (b) Torrent, M.; Duran, M.; Solá, M. Chem. Commun. 1998, 999.
31. (c) Torrent, M.; Duran, M.; Solá, M. J. Am. Chem. Soc. 1999, 121, 1309.
32. (a) Wulff, W. D.; Gilbert, A. M.; Hsung, R. P.; Rahm. A J. Org. Chem. 1995, 60, 4566.
33. (b) Barluenga, J.; López, L. A.; Martínez, S.; Tomás, M. J. Org. Chem. 1998, 63, 7588.
34. A preliminary account of this report has been published: Barluenga, J.; Aznar, F.; Martín, A.; García-Granda, S.; Pérez-Carreño, E. J. Am. Chem. Soc. 1994, 116, 11191.
35. This behavior has been previously reported: (a) Anderson, B. A.; Wulff, W. D.; Powers, T. S.; Tribbitt, S.; Rheingold, A. L. J. Am. Chem. Soc. 1992, 114, 10784. (b) Fischer, E. O.; Heckl, B.; Werner, H. J. Organomet. Chem. 1971, 28, 359. (c) Chelain, E.; Goumont, R.; Hamon, L.; Parlier, A.; Rudler, M.; Rudler, H.; Daran, J.-C.; Vaissermann, J. J. Am. Chem. Soc. 1992, 114, 8088.
36. This behavior has been previously reported: (a) Anderson, B. A.; Wulff, W. D.; Powers, T. S.; Tribbitt, S.; Rheingold, A. L. J. Am. Chem. Soc. 1992, 114, 10784. (b) Fischer, E. O.; Heckl, B.; Werner, H. J. Organomet. Chem. 1971, 28, 359. (c) Chelain, E.; Goumont, R.; Hamon, L.; Parlier, A.; Rudler, M.; Rudler, H.; Daran, J.-C.; Vaissermann, J. J. Am. Chem. Soc. 1992, 114, 8088.
37. This behavior has been previously reported: (a) Anderson, B. A.; Wulff, W. D.; Powers, T. S.; Tribbitt, S.; Rheingold, A. L. J. Am. Chem. Soc. 1992, 114, 10784. (b) Fischer, E. O.; Heckl, B.; Werner, H. J. Organomet. Chem. 1971, 28, 359. (c) Chelain, E.; Goumont, R.; Hamon, L.; Parlier, A.; Rudler, M.; Rudler, H.; Daran, J.-C.; Vaissermann, J. J. Am. Chem. Soc. 1992, 114, 8088.
38. Barluenga, J.; Aznar, F.; Martín, A. Organometallics 1995, 14, 1429.
39. The main photoprocess of Fischer carbene complexes is the decarbonylation: (a) Foley, H. C.; Strubinger, L. M.; Targos, T. S.; Geoffrey, G. L. J. Am. Chem. Soc, 1983, 105, 3064. (b) Bell, S. E. J.; Gordon, K. C.; McGarvey, J. J. J. Am. Chem. Soc. 1988, 110, 3107. (c) Knorr, J. R.; Brown, F. L. Organometallics 1994, 13, 2178.
40. The main photoprocess of Fischer carbene complexes is the decarbonylation: (a) Foley, H. C.; Strubinger, L. M.; Targos, T. S.; Geoffrey, G. L. J. Am. Chem. Soc, 1983, 105, 3064. (b) Bell, S. E. J.; Gordon, K. C.; McGarvey, J. J. J. Am. Chem. Soc. 1988, 110, 3107. (c) Knorr, J. R.; Brown, F. L. Organometallics 1994, 13, 2178.
41. The main photoprocess of Fischer carbene complexes is the decarbonylation: (a) Foley, H. C.; Strubinger, L. M.; Targos, T. S.; Geoffrey, G. L. J. Am. Chem. Soc, 1983, 105, 3064. (b) Bell, S. E. J.; Gordon, K. C.; McGarvey, J. J. J. Am. Chem. Soc. 1988, 110, 3107. (c) Knorr, J. R.; Brown, F. L. Organometallics 1994, 13, 2178.
42. Garret, K. E.; Sheridan, J. B.; Pourreau, D. B.; Feng, W. C.; Geoffrey, G. L.; Staley, D. L.; Rheingold, A. L. J. Am. Chem. Soc. 1989, 111, 8383.
43. 3-vinyl carbenes, see: Mitsudo, T. Bull. Chem. Soc. Jpn. 1998, 71, 1525.
44. 11
45. 13C NMR chemical shifts are identical is fortuitous, since both carbon atoms have different environments due to the substituents in the double bond. For example, these carbon atoms have different chemical shifts in complex 5a (see Experimental Section).
46. Grotjahn, D. B.; Dötz, K. H. Synlett 1991, 381.
47. Hepp, W.; Schubert, U. J. Orgamnnet. Chem. 1990, 385, 221.
48. Hofmann, P.; Hämmerle, M. Angew. Chem., Int. Ed. Engl. 1989, 28, 908.
49. 13C NMR chemical shift (224 ppm), are intermediate between those of standard Fischer aminovinyl carbene complexes and those reported for B-phosphoniumalkyl-and α-imoniumalkylpentacarbonylchromates. (a) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (b) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrin, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695.
50. 13C NMR chemical shift (224 ppm), are intermediate between those of standard Fischer aminovinyl carbene complexes and those reported for B-phosphoniumalkyl- and α-imoniumalkylpentacarbonylchromates. (a) Aumann, R.; Jasper, B.; Läge, M.; Krebs, B. Chem. Ber. 1994, 127, 2475. (b) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrin, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695.
51. Dvorák, D.; Ludwig, M. Organometallics 1998, 17, 3627.
52. (a) Aumann, R.; Fischer, E. O. Angew. Chem., Int. Ed. Engl. 1967, 6, 879.
53. (b) Aumann, R.; Fischer, E. O. Chem. Ber. 1968, 101, 954.
54. This stabilization has been previously postulated: Harvey, D. F.; Grenzer, E. M.; Gantzel, P. K. J. Am. Chem. Soc. 1994, 116, 6719.
55. We are aware that, although the most stable form of tetracarbonyl dienylcarbene complexes is 9 and not IV, it is this one which should be formed initially from insertion of acetylene, and, if an equilibrium between both isomers occurs, complexes IV might be also the reactive species.
56. Aumann, R.; Nienaber, H. Adv. Organomet. Chem. 1997, 41, 163.
57. 3Cr adducts of the hydroxyl free phenol can be obtained with the suitable workup of the reaction, by oxygen-free chromatography or crystallization from the reaction crude material. Nevertheless, better yields are obtained by oxidative cleavage of the chromium-arene bond in mild conditions (air and sunlight) followed by silica gel chromatography to yield the metal-free phenol.
58. (a) Mitsudo, T.; Fujita, K.; Nagano, S.; Suzuki, T.; Watanabe, Y.; Masuda, H. Organometallics 1995, 14, 4228.
59. (b) Park, J.; Kim, J. Organometallics 1995, 14, 4341.
60. 1-dienylcarbene to a phenol has been observed: Barluenga, J.; Aznar, F.; Palomero, M. A.; Barluenga, S. Org. Lett. 1999, 1, 541.
61. Dörwald, F. Z. Metal Carbenes in Organic Synthesis; Wiley-VCH: Weinheim, 1999.
62. 11
63. 11
64. 13c
65. 13C chemical shift of the carbene carbon in these species (e.g., 246 ppm for 9a). (40) A similar attack has been proposed for the [4 + 1] reaction of chromium phenylmethoxycarbene with 2-methyl-1,3-dimorpholino-1,3-butadiene. Barluenga, J.; Aznar, F.; Fernández, M. Chem. Eur. J. 1997, 3, 1629.
66. The formation of VIII from XI′ could also take place through a Nazarov-type reaction. Yamashita, A. Tetrahedron Lett. 1986, 27, 5915.
67. 13c
68. (a) Grant, D. F.; Gabe, E. J. J. Appl. Crystallogr. 1978, 11, 114.
69. (b) Lehman, M. S.; Larsen, F. K. Acta Crystallogr. 1974, A30, 580.
70. Gutiérrez-Rodríguez, A.; Aguirre-Pérez, A.; García-Granda, S. THE REFLEX V 1.2 E 2 Manual del usuario; Departamento de Química Física y Analítica, Universidad de Oviedo, 19XX.
71. García-Granda, S.; Gould, R. O.; Smits, J. M. M.; Smukalla, C.; Beurkens, P. T.; Admiraall, G.; Beurskens, G.; Bosman, W. P. DIRDIF user's guide Technical report; Crystallography Laboratory: University of Nijmegen, The Netherlands, 19XX.
72. Sheldrick, G. M. SHELXS-97: University of Göttingen, Germany, 19XX.
73. International Tables for X-Ray Crystallography; Birmingham Kynoch Press: Birmingham, UK, 1974 (present distributor, Kluwer Academic Publishers: Dordrecht); Vol. IV.