Diastereoselective intermolecular cyclopropanation of simple alkenes by fischer alkenyl and heteroaryl carbene complexes of chromium: Scope and limitations

Journal of the American Chemical Society

Volumn 122, Issue 34, 2000, Pages 8145-8154

  Barluenga, José ^a   López, Salomé ^a   Trabanco, Andrés A ^a   Fernández Acebes, Alvaro ^a   Flórez, Josefa ^a  

^a UNIVERSITY OF OVIEDO   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; ALKENYL GROUP; CARBENE; CHROMIUM DERIVATIVE; CYCLOPROPANE DERIVATIVE;

ARTICLE; CHEMICAL BOND; CHEMICAL INTERACTION; CHEMICAL STRUCTURE; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0039925723     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja000694b     Document Type: Article

References (96)

1. Reviews: (a) Brookhart, M.; Studabaker, W. B. Chem. Rev. 1987, 87, 411. (b) Reissig, H-U. In Organometallics in Organic Synthesis; Werner, H., Erker, G., Eds.; Springer: Berlin, 1989; Vol. 2, pp 311 -322. (c) Doyle, M. P. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, 1995; Vol. 12, pp 387- 420. (d) Harvey, D. F.; Sigano, D. M. Chem. Rev. 1996, 96, 271.
2. Reviews: (a) Brookhart, M.; Studabaker, W. B. Chem. Rev. 1987, 87, 411. (b) Reissig, H-U. In Organometallics in Organic Synthesis; Werner, H., Erker, G., Eds.; Springer: Berlin, 1989; Vol. 2, pp 311 -322. (c) Doyle, M. P. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, 1995; Vol. 12, pp 387- 420. (d) Harvey, D. F.; Sigano, D. M. Chem. Rev. 1996, 96, 271.
3. Reviews: (a) Brookhart, M.; Studabaker, W. B. Chem. Rev. 1987, 87, 411. (b) Reissig, H-U. In Organometallics in Organic Synthesis; Werner, H., Erker, G., Eds.; Springer: Berlin, 1989; Vol. 2, pp 311 -322. (c) Doyle, M. P. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, 1995; Vol. 12, pp 387-420. (d) Harvey, D. F.; Sigano, D. M. Chem. Rev. 1996, 96, 271.
4. Reviews: (a) Brookhart, M.; Studabaker, W. B. Chem. Rev. 1987, 87, 411. (b) Reissig, H-U. In Organometallics in Organic Synthesis; Werner, H., Erker, G., Eds.; Springer: Berlin, 1989; Vol. 2, pp 311 -322. (c) Doyle, M. P. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, 1995; Vol. 12, pp 387- 420. (d) Harvey, D. F.; Sigano, D. M. Chem. Rev. 1996, 96, 271.
5. (a) Fischer, E. O.; Dötz, K. H. Chem. Ber. 1970, 103, 1273.
6. (b) Dötz, K. H.; Fischer, E. O. Chem. Ber. 1972, 105, 1356.
7. (a) Wienand, A.; Reissig, H.-U. Tetrahedron Lett. 1988, 29, 2315.
8. (b) Herndon, J. W.; Turner, S. U. Tetrahedron Lett. 1989, 30, 4771.
9. (c) Wienand, A.; Reissig, H.-U. Organometallics 1990, 9, 3133.
10. (d) Harvey, D. F.; Brown, M. F. Tetrahedron Lett. 1990, 31, 2529.
11. (e) Wienand, A.; Reissig, H.-U. Chem. Ber. 1991, 124, 957.
12. (f) Herndon, J. W.; Turner, S. U. J. Org. Chem. 1991, 56, 286.
13. (a) Fischer, E. O.; Dötz, K. H. Chem. Ber. 1972, 105, 3966.
14. (b) Dorrer, B.; Fischer, E. O.; Kalbfus, W. J. Organomet. Chem. 1974, 81, C20.
15. (c) Wulff, W. D.; Yang, D. C.; Murray, C. K. Pure Appl. Chem. 1988, 60, 137.
16. For in situ cyclopropanations with acyloxy chromium carbene complexes, see: (d) Murray, C. K.; Yang, D. C.; Wulff, W. D. J. Am. Chem. Soc. 1990, 112, 5660.
17. For an in situ generated nonheteroatom-stabilized chromium carbene complex involved in a catalytic synthesis of spirocyclopropanes from diaryl diazo compounds and electron-rich alkenes, see: (a) Pfeiffer, J.; Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2828. (b) Pfeiffer, J.; Nieger, M.; Dötz, K. H. Eur. J. Org. Chem. 1998, 1011, 1.
18. For an in situ generated nonheteroatom-stabilized chromium carbene complex involved in a catalytic synthesis of spirocyclopropanes from diaryl diazo compounds and electron-rich alkenes, see: (a) Pfeiffer, J.; Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2828. (b) Pfeiffer, J.; Nieger, M.; Dötz, K. H. Eur. J. Org. Chem. 1998, 1011, 1.
19. (a) Cooke, M. D.; Fischer, E. O. J. Organomet. Chem. 1973, 56, 279.
20. (b) Wienand, A.; Reissig, H.-U. Angew. Chem., Int. Ed. Engl. 1990, 29, 1129.
21. See also: (c) Barluenga, J.; González, R.; Fañanás, F. J. Organometallics 1997, 16, 4525.
22. Barluenga, J.; Tomás, M.; López-Pelegrín, J. A.; Rubio, E. J. Chem. Soc., Chem. Commun. 1995, 665.
23. (a) Buchert, M.; Reissig, H.-U. Tetrahedron Lett. 1988, 29, 2319.
24. (b) Buchert, M.; Reissig, H.-U. Chem. Ber. 1992, 125, 2723.
25. (c) Buchert, M.; Hoffmann, M.; Reissig, H.-U. Chem. Ber. 1995, 128, 605.
26. (a) Harvey, D. F.; Lund, K. P. J. Am. Chem. Soc. 1991, 113, 8916.
27. See also: (b) Merlic, C. A.; Bendorf, H. D. Tetrahedron Lett. 1994, 35, 9529.
28. 5 fragment: (f) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaría, J.; Carbajo, R. J.; López-Ortiz, F.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (g) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695.
29. 5 fragment: (f) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaría, J.; Carbajo, R. J.; López-Ortiz, F.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (g) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695.
30. 5 fragment: (f) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaría, J.; Carbajo, R. J.; López-Ortiz, F.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (g) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695.
31. 5 fragment: (f) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaría, J.; Carbajo, R. J.; López-Ortiz, F.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (g) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695.
32. 5 fragment: (f) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaría, J.; Carbajo, R. J.; López-Ortiz, F.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (g) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695.
33. 5 fragment: (f) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaría, J.; Carbajo, R. J.; López-Ortiz, F.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (g) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695.
34. 5 fragment: (f) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaría, J.; Carbajo, R. J.; López-Ortiz, F.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (g) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695.
35. (11) See, for example: (a) Fischer, E. O.; Heckl, B.; Dötz, K. H.; Müller, J.; Werner, H. J. Organomet. Chem. 1969, 16, P29. (b) Hegedus, L. S. In Transition Metals in the Synthesis of Complex Organic Molecules, 2nd ed.; University Science Books: Sausalito, CA, 1999; pp 151-157.
36. (11) See, for example: (a) Fischer, E. O.; Heckl, B.; Dötz, K. H.; Müller, J.; Werner, H. J. Organomet. Chem. 1969, 16, P29. (b) Hegedus, L. S. In Transition Metals in the Synthesis of Complex Organic Molecules, 2nd ed.; University Science Books: Sausalito, CA, 1999; pp 151-157.
37. (a) Toledano, C. A.; Rudler, H.; Daran, J.-C.; Jeannin, Y. J. Chem. Soc., Chem. Commun. 1984, 574.
38. (b) Barluenga, J.; Montserrat, J. M.; Flórez, J. J. Chem. Soc., Chem. Commun. 1993, 1068.
39. (a) Casey, C. P.; Vollendorf, N. W.; Haller, K. J. J. Am. Chem. Soc. 1984, 106, 3754.
40. (b) Casey, C. P.; Shusterman, A. J. Organometallics 1985, 4, 736.
41. (c) Casey, C. P.; Hornung, N. L.; Kosar, W. P. J. Am. Chem. Soc. 1987, 109, 4908.
42. (d) Söderberg, B. C.; Hegedus, L. S. Organometallics 1990, 9, 3113.
43. (a) Casey, C. P.; Burkhardt, T. J. J. Am. Chem. Soc. 1974, 96, 7808.
44. (b) Casey, C. P.; Tuinstra, H. E.; Saeman, M. C. J. Am. Chem. Soc. 1976, 98, 608.
45. (c) Casey, C. P.; Albin, L. D.; Burkhardt, T. J. J. Am. Chem. Soc. 1977, 99, 2533.
46. (d) Harvey, D. F.; Brown, M. F. J. Am. Chem. Soc. 1990, 112, 7806.
47. (e) Fischer, H.; Hofmann, J. Chem. Ber. 1991, 124, 981.
48. (f) Fischer, H.; Volkland, H.-P.; Stumpf, R. Anal. Quím. Int. Ed. 1996, 92, 148.
49. See also: (g) Rudler, H.; Audouin, M.; Parlier, A.; Martín-Vaca, B.; Goumont, R.; Durand-Réville, T.; Vaissermann, J. J. Am. Chem. Soc. 1996, 118, 12045.
50. (h) Gunnoe, T. B.; White, P. S.; Templeton, J. L.; Casarrubios, L. J. Am. Chem. Soc. 1997, 119, 3171.
51. For intramolecular cyclopropanations of simple alkenes by non-heteroatom-stabilized carbene complexes in situ generated by previous reaction of an alkoxycarbene complex with an alkyne, see for instance: (a) Parlier, A.; Rudler, H.; Platzer, N.; Fontanille, M.; Soum, A. J. Chem. Soc., Dalton Trans. 1987, 1041. (b) Hoye, T. R.; Suriano, J. A. Organometallics 1992, 11, 2044. (c) Harvey, D. F.; Brown, M. F. J. Org. Chem. 1992, 57, 5559. (d) Harvey, D. F.; Sigano, D. M. J. Org. Chem. 1996, 61, 2268.
52. For intramolecular cyclopropanations of simple alkenes by non- heteroatom-stabilized carbene complexes in situ generated by previous reaction of an alkoxycarbene complex with an alkyne, see for instance: (a) Parlier, A.; Rudler, H.; Platzer, N.; Fontanille, M.; Soum, A. J. Chem. Soc., Dalton Trans. 1987, 1041. (b) Hoye, T. R.; Suriano, J. A. Organometallics 1992, 11, 2044. (c) Harvey, D. F.; Brown, M. F. J. Org. Chem. 1992, 57, 5559. (d) Harvey, D. F.; Sigano, D. M. J. Org. Chem. 1996, 61, 2268.
53. For intramolecular cyclopropanations of simple alkenes by non- heteroatom-stabilized carbene complexes in situ generated by previous reaction of an alkoxycarbene complex with an alkyne, see for instance: (a) Parlier, A.; Rudler, H.; Platzer, N.; Fontanille, M.; Soum, A. J. Chem. Soc., Dalton Trans. 1987, 1041. (b) Hoye, T. R.; Suriano, J. A. Organometallics 1992, 11, 2044. (c) Harvey, D. F.; Brown, M. F. J. Org. Chem. 1992, 57, 5559. (d) Harvey, D. F.; Sigano, D. M. J. Org. Chem. 1996, 61, 2268.
54. For intramolecular cyclopropanations of simple alkenes by non- heteroatom-stabilized carbene complexes in situ generated by previous reaction of an alkoxycarbene complex with an alkyne, see for instance: (a) Parlier, A.; Rudler, H.; Platzer, N.; Fontanille, M.; Soum, A. J. Chem. Soc., Dalton Trans. 1987, 1041. (b) Hoye, T. R.; Suriano, J. A. Organometallics 1992, 11, 2044. (c) Harvey, D. F.; Brown, M. F. J. Org. Chem. 1992, 57, 5559. (d) Harvey, D. F.; Sigano, D. M. J. Org. Chem. 1996, 61, 2268.
55. (a) Sierra, M. A.; Soderberg, B.; Lander, P. A.; Hegedus, L. S. Organometallics 1993, 12, 3769.
56. (b) Barluenga, J.; Aznar, F.; Martín, A. Organometallics 1995, 14, 1429.
57. Merino, I.; Hegedus, L. S. Organometallics 1995, 14, 2522.
58. For intramolecular cyclopropanation of simple alkenes with non-heteroatom-stabilized carbene complexes in situ generated by previous reaction of an aminocarbene complex with an alkyne, see: (a) Parlier, A.; Rudler, H.; Yefsah, R.; Alvarez, C. J. Organomet. Chem. 1987, 328, C21. (b) Hoye, T. R.; Rehberg, G. M. Organometallics 1989, 8, 2070. (c) Hoye, T. R.; Vyvyan, J. R. J. Org. Chem. 1995, 60, 4184.
59. For intramolecular cyclopropanation of simple alkenes with non- heteroatom-stabilized carbene complexes in situ generated by previous reaction of an aminocarbene complex with an alkyne, see: (a) Parlier, A.; Rudler, H.; Yefsah, R.; Alvarez, C. J. Organomet. Chem. 1987, 328, C21. (b) Hoye, T. R.; Rehberg, G. M. Organometallics 1989, 8, 2070. (c) Hoye, T. R.; Vyvyan, J. R. J. Org. Chem. 1995, 60, 4184.
60. For intramolecular cyclopropanation of simple alkenes with non- heteroatom-stabilized carbene complexes in situ generated by previous reaction of an aminocarbene complex with an alkyne, see: (a) Parlier, A.; Rudler, H.; Yefsah, R.; Alvarez, C. J. Organomet. Chem. 1987, 328, C21. (b) Hoye, T. R.; Rehberg, G. M. Organometallics 1989, 8, 2070. (c) Hoye, T. R.; Vyvyan, J. R. J. Org. Chem. 1995, 60, 4184.
61. Preliminary communication: Barluenga, J.; Fernández-Acebes, A.; Trabanco, A. A.; Flórez, J. J. Am. Chem. Soc. 1997, 119, 7591.
62. Ferrocenylcarbene complexes of Cr, W, and Mn were previously described: (a) Connor, J. A.; Lloyd, J. P. J. Chem. Soc., Dalton Trans. 1972, 1470. Cyclopropanation of dimethyl fumarate with the Cr derivative was reported: (b) Connor, J. A.; Lloyd, J. P. J. Chem. Soc., Perkin Trans. 1 1973, 17.
63. Ferrocenylcarbene complexes of Cr, W, and Mn were previously described: (a) Connor, J. A.; Lloyd, J. P. J. Chem. Soc., Dalton Trans. 1972, 1470. Cyclopropanation of dimethyl fumarate with the Cr derivative was reported: (b) Connor, J. A.; Lloyd, J. P. J. Chem. Soc., Perkin Trans. 1 1973, 17.
64. Complexes of these characteristics are attractive synthetic goals due to their physical and chemical properties. See, for example: (a) Togni, A.; Rihs, G. Organometallics 1993, 12, 3368. (b) Wong, W.-Y.; Wong, W.- T.; Cheung, K.-K. J. Chem. Soc., Dalton Trans. 1995, 1379. (c) Sato, M.; Mogi, E.; Katada, M. Organometallics 1995, 14, 4837. (d) Behrens, U.; Brussaard, H.; Hagenau, U.; Heck, J.; Hendrickx, E.; Körnich, J.; van der Linden, J. G. M.; Persoons, A.; Spek, A. L.; Veldman, N.; Voss, B.; Wong, H. Chem. Eur. J. 1996, 2, 98. (e) Fischer, H.; Leroux, F.; Roth, G.; Stumpf, R. Organometallics 1996, 15, 3723. (f) Jayaprakash, K. N.; Ray, P. C.; Matsuoka, I.; Bhadbhade, M. M.; Puranik, V. G.; Das, P. K.; Nishihara, H.; Sarkar, A. Organometallics 1999, 18, 3851.
65. Complexes of these characteristics are attractive synthetic goals due to their physical and chemical properties. See, for example: (a) Togni, A.; Rihs, G. Organometallics 1993, 12, 3368. (b) Wong, W.-Y.; Wong, W.-T.; Cheung, K.-K. J. Chem. Soc., Dalton Trans. 1995, 1379. (c) Sato, M.; Mogi, E.; Katada, M. Organometallics 1995, 14, 4837. (d) Behrens, U.; Brussaard, H.; Hagenau, U.; Heck, J.; Hendrickx, E.; Körnich, J.; van der Linden, J. G. M.; Persoons, A.; Spek, A. L.; Veldman, N.; Voss, B.; Wong, H. Chem. Eur. J. 1996, 2, 98. (e) Fischer, H.; Leroux, F.; Roth, G.; Stumpf, R. Organometallics 1996, 15, 3723. (f) Jayaprakash, K. N.; Ray, P. C.; Matsuoka, I.; Bhadbhade, M. M.; Puranik, V. G.; Das, P. K.; Nishihara, H.; Sarkar, A. Organometallics 1999, 18, 3851.
66. Complexes of these characteristics are attractive synthetic goals due to their physical and chemical properties. See, for example: (a) Togni, A.; Rihs, G. Organometallics 1993, 12, 3368. (b) Wong, W.-Y.; Wong, W.- T.; Cheung, K.-K. J. Chem. Soc., Dalton Trans. 1995, 1379. (c) Sato, M.; Mogi, E.; Katada, M. Organometallics 1995, 14, 4837. (d) Behrens, U.; Brussaard, H.; Hagenau, U.; Heck, J.; Hendrickx, E.; Körnich, J.; van der Linden, J. G. M.; Persoons, A.; Spek, A. L.; Veldman, N.; Voss, B.; Wong, H. Chem. Eur. J. 1996, 2, 98. (e) Fischer, H.; Leroux, F.; Roth, G.; Stumpf, R. Organometallics 1996, 15, 3723. (f) Jayaprakash, K. N.; Ray, P. C.; Matsuoka, I.; Bhadbhade, M. M.; Puranik, V. G.; Das, P. K.; Nishihara, H.; Sarkar, A. Organometallics 1999, 18, 3851.
67. Complexes of these characteristics are attractive synthetic goals due to their physical and chemical properties. See, for example: (a) Togni, A.; Rihs, G. Organometallics 1993, 12, 3368. (b) Wong, W.-Y.; Wong, W.- T.; Cheung, K.-K. J. Chem. Soc., Dalton Trans. 1995, 1379. (c) Sato, M.; Mogi, E.; Katada, M. Organometallics 1995, 14, 4837. (d) Behrens, U.; Brussaard, H.; Hagenau, U.; Heck, J.; Hendrickx, E.; Körnich, J.; van der Linden, J. G. M.; Persoons, A.; Spek, A. L.; Veldman, N.; Voss, B.; Wong, H. Chem. Eur. J. 1996, 2, 98. (e) Fischer, H.; Leroux, F.; Roth, G.; Stumpf, R. Organometallics 1996, 15, 3723. (f) Jayaprakash, K. N.; Ray, P. C.; Matsuoka, I.; Bhadbhade, M. M.; Puranik, V. G.; Das, P. K.; Nishihara, H.; Sarkar, A. Organometallics 1999, 18, 3851.
68. Complexes of these characteristics are attractive synthetic goals due to their physical and chemical properties. See, for example: (a) Togni, A.; Rihs, G. Organometallics 1993, 12, 3368. (b) Wong, W.-Y.; Wong, W.- T.; Cheung, K.-K. J. Chem. Soc., Dalton Trans. 1995, 1379. (c) Sato, M.; Mogi, E.; Katada, M. Organometallics 1995, 14, 4837. (d) Behrens, U.; Brussaard, H.; Hagenau, U.; Heck, J.; Hendrickx, E.; Körnich, J.; van der Linden, J. G. M.; Persoons, A.; Spek, A. L.; Veldman, N.; Voss, B.; Wong, H. Chem. Eur. J. 1996, 2, 98. (e) Fischer, H.; Leroux, F.; Roth, G.; Stumpf, R. Organometallics 1996, 15, 3723. (f) Jayaprakash, K. N.; Ray, P. C.; Matsuoka, I.; Bhadbhade, M. M.; Puranik, V. G.; Das, P. K.; Nishihara, H.; Sarkar, A. Organometallics 1999, 18, 3851.
69. Complexes of these characteristics are attractive synthetic goals due to their physical and chemical properties. See, for example: (a) Togni, A.; Rihs, G. Organometallics 1993, 12, 3368. (b) Wong, W.-Y.; Wong, W.- T.; Cheung, K.-K. J. Chem. Soc., Dalton Trans. 1995, 1379. (c) Sato, M.; Mogi, E.; Katada, M. Organometallics 1995, 14, 4837. (d) Behrens, U.; Brussaard, H.; Hagenau, U.; Heck, J.; Hendrickx, E.; Körnich, J.; van der Linden, J. G. M.; Persoons, A.; Spek, A. L.; Veldman, N.; Voss, B.; Wong, H. Chem. Eur. J. 1996, 2, 98. (e) Fischer, H.; Leroux, F.; Roth, G.; Stumpf, R. Organometallics 1996, 15, 3723. (f) Jayaprakash, K. N.; Ray, P. C.; Matsuoka, I.; Bhadbhade, M. M.; Puranik, V. G.; Das, P. K.; Nishihara, H.; Sarkar, A. Organometallics 1999, 18, 3851.
70. Vinylcyclopropanes are recognized to have high synthetic potential: (a) Reissig, H.-U. Angew. Chem., Int. Ed. Engl. 1996, 35, 971. (b) Tang, Y.; Huang, Y.-Z.; Dai, L.-X.; Chi, Z-F.; Shi, L.-P. J. Org. Chem. 1996, 61, 5762.
71. Vinylcyclopropanes are recognized to have high synthetic potential: (a) Reissig, H.-U. Angew. Chem., Int. Ed. Engl. 1996, 35, 971. (b) Tang, Y.; Huang, Y.-Z.; Dai, L.-X.; Chi, Z-F.; Shi, L.-P. J. Org. Chem. 1996, 61, 5762.
72. Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587.
73. This preference has precedents. For example, see ref 1b.
74. Indeed, carbene complex 1 reacted smoothly with 1-hexyne following the Dötz reaction pathway to give regioselectively 2-butyl-6-ferrocenyl-4-methoxyphenol (12). graph presented The structure of phenols 11 and 12, which corresponds to the expected regioisomer in the Dötz benzannulation reaction with terminal alkynes, was clearly established from the value of the coupling constant between the aromatic protons (J = 3.0-3.1 Hz), which indicates a meta relative disposition of these hydrogens.
75. (a) Veysoglu, T.; Mitscher, L. A.; Swayze, J. K. Synthesis 1980, 807.
76. (b) Hanessian, S.; Andreotti, D.; Gomtsyan, A. J. Am. Chem. Soc. 1995, 117, 10393.
77. The major diastereoisomer was previously separated by column chromatography.
78. The relative instability of the molybdenum carbene complexes compared to chromium and tungsten derivatives is known: see ref 3d.
79. The reduced bias of tungsten carbene complexes to undergo cyclopropanation reactions in relation to chromium carbene derivatives has precedents: see refs 4c, 9, and Barluenga, J.; Aznar, F.; Martín, A.; Barluenga, S.; García-Granda, S.; Paneque-Quevedo, A. A. J. Chem. Soc., Chem. Commun. 1994, 843.
80. 13C) 2D correlation experiments: heteronuclear multiple quantum coherence (HMQC) and heteronuclear multiple-bond correlation (HMBC).
81. Yoshida, Y.; Sakakura, Y.; Aso, N.; Okada, S.; Tanabe, Y. Tetrahedron 1999, 55, 2183.
82. Casey, C. P.; Cesa, M. C. Organometallics 1982, 1, 87.
83. 3-allylidene complexes, see: (d) Mitsudo, T. Bull. Chem. Soc. Jpn. 1998, 71, 1525.
84. 3-allylidene complexes, see: (d) Mitsudo, T. Bull. Chem. Soc. Jpn. 1998, 71, 1525.
85. 3-allylidene complexes, see: (d) Mitsudo, T. Bull. Chem. Soc. Jpn. 1998, 71, 1525.
86. 3-allylidene complexes, see: (d) Mitsudo, T. Bull. Chem. Soc. Jpn. 1998, 71, 1525.
87. This equilibrium has been previously identified by a density functional study and by NMR analysis; see, respectively: (a) Gleichmann, M. M.; Dötz, K. H.; Hess, B. A. J. Am. Chem. Soc. 1996, 118, 10551. (b) Barluenga, J.; Aznar, F.; Gutiérrez, I.; Martín, A.; García-Granda, S.; LLorca-Baragaño, M. A. J. Am. Chem. Soc. 2000, 122, 1314.
88. This equilibrium has been previously identified by a density functional study and by NMR analysis; see, respectively: (a) Gleichmann, M. M.; Dötz, K. H.; Hess, B. A. J. Am. Chem. Soc. 1996, 118, 10551. (b) Barluenga, J.; Aznar, F.; Gutiérrez, I.; Martín, A.; García-Granda, S.; LLorca-Baragaño, M. A. J. Am. Chem. Soc. 2000, 122, 1314.
89. In addition, the aromatic nature of carbene complex VI will decrease its reactivity as indicated by the high thermal stability of this complex.
90. This regioselectivity could be predicted based on the polarization of both the olefin carbon-carbon double bond and metal-carbene carbon bond of the carbene complex and is the one deduced from the constitution of formal insertion-hydrolysis products 26, 28, and 38.
91. Hoffmann, M.; Reissig, H.-U. Synlett 1995, 625.
92. Doyle, M. P.; Griffin, J. H.; Bagheri, V.; Dorow, R. L. Organametallics 1984, 3, 53.
93. Alternatively, the non existing diastereoselectivity in the cyclopropanation reaction of trans-2-pentene could be due to low regioselectivity in the formation of the corresponding metallacyclobutanes 56. This trans olefin with two similar substituents could form two regioisomeric metallacyclobutane intermediates of comparable stability which finally would lead to two different diastereoisomers. In this case, it can be said that this cyclopropanation reaction of cis and trans olefins is stereospecific. We thank one of the referees for calling our attention to this possibility.
94. It was suggested that enol ethers similar to 61 are formed by acid-catalyzed rearrangement from the corresponding donor-acceptor-substituted cyclopropanes: see ref 3c.
95. 1H NMR analysis of the crude reaction mixtures suggested the presence of 61 (a triplet signal appearing at δ 4.80 (precursor of 26), 4.92 (precursor of 28), 5.00 (precursor of 38) and a multiplet at 2.30 (precursor of 26), 2.06 (precursor of 28), or doublet signal at 3.69 (precursor of 38)).
96. General information, experimental procedures, and spectral data for compounds not described here are provided in the Supporting Information.