[3 + 2] Annulation of Allylidenetriphenylphosphorane with 1,2-Diacylethylenes and 1,2-Diacylacetylenes: A One-Step Synthesis of Tri- and Tetrasubstituted Cyclopentadienes and Fulvenes

Journal of Organic Chemistry

Volumn 62, Issue 19, 1997, Pages 6529-6538

  Himeda, Yuichiro ^a   Yamataka, Hiroshi ^b   Ueda, Ikuo ^b   Hatanaka, Minoru ^c  

^a NATL INST OF MAT AND CHEM RES   (Japan)

^b OSAKA UNIVERSITY   (Japan)

^c UNIVERSITY OF FUKUI   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

BENZENE DERIVATIVE; CYCLOPENTADIENE DERIVATIVE; PHOSPHORANE DERIVATIVE;

ALKYLATION; ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLIZATION; DIMERIZATION; ISOMERISM; NUCLEAR OVERHAUSER EFFECT; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; SYNTHESIS; THERMODYNAMICS;

EID: 0030879713     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970594x     Document Type: Article

References (88)

1. For some leading references, see: (a) Fringuelli, F.; Taticchi, A. Dienes in the Diets-Alder Reaction; John Wiley & Sons, Inc.: New York, 1990. (b) Corey, E. J.; Ravindranathan, T.; Terashima, S. J. Am. Chem. Soc. 1971, 93, 4326-4327. (c) Breitholle, E. G.; Fallis, A. G. J. Org. Chem. 1978, 43, 1964-1968. (d) Landry, D. W. Tetrahedron 1983, 39, 2761-2768. (e) Gallacher, G.; Ng, A. S.; Attah-Poku, S. K.; Antczak, K.; Alward, S. J.; Kingston, J. F.; Fallis, A. G. Can. J. Chem. 1984, 62, 1709-1716. (f) Stille, J. R.; Grubbs, R. H. J. Org. Chem. 1989, 54, 434-444. (g) Sternbach, D. D.; Ensinger, C. L. J. Org. Chem. 1990, 55, 2725-2736. (h) Lei, B.; Fallis, A. G. J. Am. Chem, Soc. 1990, 112, 4609-4610.
2. For some leading references, see: (a) Fringuelli, F.; Taticchi, A. Dienes in the Diets-Alder Reaction; John Wiley & Sons, Inc.: New York, 1990. (b) Corey, E. J.; Ravindranathan, T.; Terashima, S. J. Am. Chem. Soc. 1971, 93, 4326-4327. (c) Breitholle, E. G.; Fallis, A. G. J. Org. Chem. 1978, 43, 1964-1968. (d) Landry, D. W. Tetrahedron 1983, 39, 2761-2768. (e) Gallacher, G.; Ng, A. S.; Attah-Poku, S. K.; Antczak, K.; Alward, S. J.; Kingston, J. F.; Fallis, A. G. Can. J. Chem. 1984, 62, 1709-1716. (f) Stille, J. R.; Grubbs, R. H. J. Org. Chem. 1989, 54, 434-444. (g) Sternbach, D. D.; Ensinger, C. L. J. Org. Chem. 1990, 55, 2725-2736. (h) Lei, B.; Fallis, A. G. J. Am. Chem, Soc. 1990, 112, 4609-4610.
3. For some leading references, see: (a) Fringuelli, F.; Taticchi, A. Dienes in the Diets-Alder Reaction; John Wiley & Sons, Inc.: New York, 1990. (b) Corey, E. J.; Ravindranathan, T.; Terashima, S. J. Am. Chem. Soc. 1971, 93, 4326-4327. (c) Breitholle, E. G.; Fallis, A. G. J. Org. Chem. 1978, 43, 1964-1968. (d) Landry, D. W. Tetrahedron 1983, 39, 2761-2768. (e) Gallacher, G.; Ng, A. S.; Attah-Poku, S. K.; Antczak, K.; Alward, S. J.; Kingston, J. F.; Fallis, A. G. Can. J. Chem. 1984, 62, 1709-1716. (f) Stille, J. R.; Grubbs, R. H. J. Org. Chem. 1989, 54, 434-444. (g) Sternbach, D. D.; Ensinger, C. L. J. Org. Chem. 1990, 55, 2725-2736. (h) Lei, B.; Fallis, A. G. J. Am. Chem, Soc. 1990, 112, 4609-4610.
4. For some leading references, see: (a) Fringuelli, F.; Taticchi, A. Dienes in the Diets-Alder Reaction; John Wiley & Sons, Inc.: New York, 1990. (b) Corey, E. J.; Ravindranathan, T.; Terashima, S. J. Am. Chem. Soc. 1971, 93, 4326-4327. (c) Breitholle, E. G.; Fallis, A. G. J. Org. Chem. 1978, 43, 1964-1968. (d) Landry, D. W. Tetrahedron 1983, 39, 2761-2768. (e) Gallacher, G.; Ng, A. S.; Attah-Poku, S. K.; Antczak, K.; Alward, S. J.; Kingston, J. F.; Fallis, A. G. Can. J. Chem. 1984, 62, 1709-1716. (f) Stille, J. R.; Grubbs, R. H. J. Org. Chem. 1989, 54, 434-444. (g) Sternbach, D. D.; Ensinger, C. L. J. Org. Chem. 1990, 55, 2725-2736. (h) Lei, B.; Fallis, A. G. J. Am. Chem, Soc. 1990, 112, 4609-4610.
5. For some leading references, see: (a) Fringuelli, F.; Taticchi, A. Dienes in the Diets-Alder Reaction; John Wiley & Sons, Inc.: New York, 1990. (b) Corey, E. J.; Ravindranathan, T.; Terashima, S. J. Am. Chem. Soc. 1971, 93, 4326-4327. (c) Breitholle, E. G.; Fallis, A. G. J. Org. Chem. 1978, 43, 1964-1968. (d) Landry, D. W. Tetrahedron 1983, 39, 2761-2768. (e) Gallacher, G.; Ng, A. S.; Attah-Poku, S. K.; Antczak, K.; Alward, S. J.; Kingston, J. F.; Fallis, A. G. Can. J. Chem. 1984, 62, 1709-1716. (f) Stille, J. R.; Grubbs, R. H. J. Org. Chem. 1989, 54, 434-444. (g) Sternbach, D. D.; Ensinger, C. L. J. Org. Chem. 1990, 55, 2725-2736. (h) Lei, B.; Fallis, A. G. J. Am. Chem, Soc. 1990, 112, 4609-4610.
6. For some leading references, see: (a) Fringuelli, F.; Taticchi, A. Dienes in the Diets-Alder Reaction; John Wiley & Sons, Inc.: New York, 1990. (b) Corey, E. J.; Ravindranathan, T.; Terashima, S. J. Am. Chem. Soc. 1971, 93, 4326-4327. (c) Breitholle, E. G.; Fallis, A. G. J. Org. Chem. 1978, 43, 1964-1968. (d) Landry, D. W. Tetrahedron 1983, 39, 2761-2768. (e) Gallacher, G.; Ng, A. S.; Attah-Poku, S. K.; Antczak, K.; Alward, S. J.; Kingston, J. F.; Fallis, A. G. Can. J. Chem. 1984, 62, 1709-1716. (f) Stille, J. R.; Grubbs, R. H. J. Org. Chem. 1989, 54, 434-444. (g) Sternbach, D. D.; Ensinger, C. L. J. Org. Chem. 1990, 55, 2725-2736. (h) Lei, B.; Fallis, A. G. J. Am. Chem, Soc. 1990, 112, 4609-4610.
7. For some leading references, see: (a) Fringuelli, F.; Taticchi, A. Dienes in the Diets-Alder Reaction; John Wiley & Sons, Inc.: New York, 1990. (b) Corey, E. J.; Ravindranathan, T.; Terashima, S. J. Am. Chem. Soc. 1971, 93, 4326-4327. (c) Breitholle, E. G.; Fallis, A. G. J. Org. Chem. 1978, 43, 1964-1968. (d) Landry, D. W. Tetrahedron 1983, 39, 2761-2768. (e) Gallacher, G.; Ng, A. S.; Attah-Poku, S. K.; Antczak, K.; Alward, S. J.; Kingston, J. F.; Fallis, A. G. Can. J. Chem. 1984, 62, 1709-1716. (f) Stille, J. R.; Grubbs, R. H. J. Org. Chem. 1989, 54, 434-444. (g) Sternbach, D. D.; Ensinger, C. L. J. Org. Chem. 1990, 55, 2725-2736. (h) Lei, B.; Fallis, A. G. J. Am. Chem, Soc. 1990, 112, 4609-4610.
8. For some leading references, see: (a) Fringuelli, F.; Taticchi, A. Dienes in the Diets-Alder Reaction; John Wiley & Sons, Inc.: New York, 1990. (b) Corey, E. J.; Ravindranathan, T.; Terashima, S. J. Am. Chem. Soc. 1971, 93, 4326-4327. (c) Breitholle, E. G.; Fallis, A. G. J. Org. Chem. 1978, 43, 1964-1968. (d) Landry, D. W. Tetrahedron 1983, 39, 2761-2768. (e) Gallacher, G.; Ng, A. S.; Attah-Poku, S. K.; Antczak, K.; Alward, S. J.; Kingston, J. F.; Fallis, A. G. Can. J. Chem. 1984, 62, 1709-1716. (f) Stille, J. R.; Grubbs, R. H. J. Org. Chem. 1989, 54, 434-444. (g) Sternbach, D. D.; Ensinger, C. L. J. Org. Chem. 1990, 55, 2725-2736. (h) Lei, B.; Fallis, A. G. J. Am. Chem, Soc. 1990, 112, 4609-4610.
9. For some leading reviews, see: (a) Slocum, D. W.; Ernst, C. R. Adv. Organomet. Chem. 1972, 10, 79-114. (b) Macomber, D. W.; Hart, W. P.; Rausch, M. D. Adv. Organomet. Chem. 1982, 21, 1-55. Haltermann, R. L. Chem. Rev. 1992, 92, 965-994. Ewing, D. F. Rodd's Chemistry of Carbon Compounds, 2nd ed.; Sainsbury, M., Eds.; Elsevier Science Publishers: Amsterdam, 1992; Vol. 2A and B, Chapter 4c.
10. For some leading reviews, see: (a) Slocum, D. W.; Ernst, C. R. Adv. Organomet. Chem. 1972, 10, 79-114. (b) Macomber, D. W.; Hart, W. P.; Rausch, M. D. Adv. Organomet. Chem. 1982, 21, 1-55. Haltermann, R. L. Chem. Rev. 1992, 92, 965-994. Ewing, D. F. Rodd's Chemistry of Carbon Compounds, 2nd ed.; Sainsbury, M., Eds.; Elsevier Science Publishers: Amsterdam, 1992; Vol. 2A and B, Chapter 4c.
11. For some leading reviews, see: (a) Slocum, D. W.; Ernst, C. R. Adv. Organomet. Chem. 1972, 10, 79-114. (b) Macomber, D. W.; Hart, W. P.; Rausch, M. D. Adv. Organomet. Chem. 1982, 21, 1-55. Haltermann, R. L. Chem. Rev. 1992, 92, 965-994. Ewing, D. F. Rodd's Chemistry of Carbon Compounds, 2nd ed.; Sainsbury, M., Eds.; Elsevier Science Publishers: Amsterdam, 1992; Vol. 2A and B, Chapter 4c.
12. For some leading reviews, see: (a) Slocum, D. W.; Ernst, C. R. Adv. Organomet. Chem. 1972, 10, 79-114. (b) Macomber, D. W.; Hart, W. P.; Rausch, M. D. Adv. Organomet. Chem. 1982, 21, 1-55. Haltermann, R. L. Chem. Rev. 1992, 92, 965-994. Ewing, D. F. Rodd's Chemistry of Carbon Compounds, 2nd ed.; Sainsbury, M., Eds.; Elsevier Science Publishers: Amsterdam, 1992; Vol. 2A and B, Chapter 4c.
13. (a) Rigby, J. H. Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 5, pp 626.
14. (b) Fleming, I. Frontier Orbitals and Organic Chemical Reactions; John Wiley & Sons, Inc.: New York, 1985; pp 178-181.
15. (c) Wang, Y.; Mukherjee, D.; Birney, D.; Houk, K. N. J. Org. Chem. 1990, 55, 4504-4506.
16. (d) Coe, J. W.; Vetelino, M. G.; Kemp, D. S. Tetrahedron Lett. 1994, 35, 6627-6630.
17. (a) For an exellent review, see: Zeller, K.-P. Pentafulvenes. In Methoden der Organischen Chemie; Georg Thieme Verlag: Stuttgart, 1985; Vol. 5/2C, pp 504-684.
18. (b) Buchi, G.; Berthet, D.; Decorzant, R.; Grieder, A.; Hauser, A. J. Org. Chem. 1976, 41, 3208-3209.
19. (c) Stone, K. J.; Little, R. D. J. Org. Chem. 1984, 49, 1849-1853.
20. (d) Jacobs, S. J.; Schulz, S. A.; Javin, R.; Novak, J.; Dougherty, D. A. J. Am. Chem. Soc. 1993, 115, 1744-1753.
21. (e) Erden, I.; Xu, F.-P.; Sadoun, A.; Smith, W.; Sheff, G.; Ossun, M. J. Org. Chem. 1995, 60, 813-820 and references cited therein.
22. (a) Alder, K.; Ache, H.-J. Chem. Ber. 1962, 95, 503-510.
23. (b) McLean, S.; Hayes, P. Tetrahedron 1965, 21, 2313-2327.
24. (c) Bergmann, E. D. Chem. Rev. 1968, 68, 41-84.
25. (d) Hafner, K.; Thiele, G. F.; Mink, C. Angew. Chem., Int. Ed. Engl. 1988, 27, 1191-1192.
26. (e) Jutzi, P.; Dahlhaus, J. Synthesis 1993, 684-686.
27. (a) Threlkel, R. S.; Bercaw, J. E. J. Organomet. Chem. 1977, 136, 1-5.
28. (b) Wochner, F.; Zsolnai, L.; Huttner, G.; Brintzinger, H. H. J. Organomet. Chem. 1985, 288, 69-77.
29. (c) Stein, D.; Sitzmann, H. J. Organomet. Chem. 1991, 402, C1-C3.
30. (d) Garner, C. M.; Prince, M. E. Tetrahedron Lett. 1994, 35, 2463-2464.
31. Zair, T.; Santelli-Rouvier, C.; Santelli, M. Tetrahedron 1993, 49, 3313-3324.
32. (a) Scattebol, L. Chem. Ind. 1962, 2146-2147; Tetrahedron 1967, 23, 1107-1117.
33. (a) Scattebol, L. Chem. Ind. 1962, 2146-2147; Tetrahedron 1967, 23, 1107-1117.
34. (b) Holm, K. H.; Scattebol, L. Acta Chem. Scand. Ser. B 1985, 39, 549-561.
35. (d) Paquette, L. A.; Gugelchuk, M.; McLaughlin M. L. J. Org. Chem. 1987, 52, 4932-4940.
36. (c) Baird, M. S.; Jefferies, I. Tetrahedron Lett. 1986, 27, 2493-2496.
37. (a) Aumann, R.; Heinen, H.; Dartmann, M.; Krebs, B. Chem. Ber. 1991, 124, 2343-2347.
38. (b) Flynn, B. L.; Funk, F. J.; Silveira, C. C.; de Meijere, A. Synlett 1995, 1007-1010.
39. (c) Aumann, R.; Meyer, A. G.; Frohlich, R. Organometallics 1996, 15, 5018-5027.
40. For other interesting cyclization, see: (a) Feitler, D.; Whitesides, G. M. Inorg. Chem. 1976, 15, 466-469. (b) Sekiya, A.; Stille, J. K. J. Am. Chem. Soc. 1981, 103, 5096-5100. (c) Koschinsky, R.; Kohli, T.-P.; Mayr, H. Tetrahedron Lett. 1988, 29, 5641-5644. (d) Lee, B. Y.; Moon, H.; Chung Y. K. J. Am. Chem. Soc. 1994, 116, 2163-2164. (e) Takahashi, T.; Xi, Z.; Kotora, M.; Xi, C. Tetrahedron Lett. 1996, 37, 7521-7524.
41. For other interesting cyclization, see: (a) Feitler, D.; Whitesides, G. M. Inorg. Chem. 1976, 15, 466-469. (b) Sekiya, A.; Stille, J. K. J. Am. Chem. Soc. 1981, 103, 5096-5100. (c) Koschinsky, R.; Kohli, T.-P.; Mayr, H. Tetrahedron Lett. 1988, 29, 5641-5644. (d) Lee, B. Y.; Moon, H.; Chung Y. K. J. Am. Chem. Soc. 1994, 116, 2163-2164. (e) Takahashi, T.; Xi, Z.; Kotora, M.; Xi, C. Tetrahedron Lett. 1996, 37, 7521-7524.
42. For other interesting cyclization, see: (a) Feitler, D.; Whitesides, G. M. Inorg. Chem. 1976, 15, 466-469. (b) Sekiya, A.; Stille, J. K. J. Am. Chem. Soc. 1981, 103, 5096-5100. (c) Koschinsky, R.; Kohli, T.-P.; Mayr, H. Tetrahedron Lett. 1988, 29, 5641-5644. (d) Lee, B. Y.; Moon, H.; Chung Y. K. J. Am. Chem. Soc. 1994, 116, 2163-2164. (e) Takahashi, T.; Xi, Z.; Kotora, M.; Xi, C. Tetrahedron Lett. 1996, 37, 7521-7524.
43. For other interesting cyclization, see: (a) Feitler, D.; Whitesides, G. M. Inorg. Chem. 1976, 15, 466-469. (b) Sekiya, A.; Stille, J. K. J. Am. Chem. Soc. 1981, 103, 5096-5100. (c) Koschinsky, R.; Kohli, T.-P.; Mayr, H. Tetrahedron Lett. 1988, 29, 5641-5644. (d) Lee, B. Y.; Moon, H.; Chung Y. K. J. Am. Chem. Soc. 1994, 116, 2163-2164. (e) Takahashi, T.; Xi, Z.; Kotora, M.; Xi, C. Tetrahedron Lett. 1996, 37, 7521-7524.
44. For other interesting cyclization, see: (a) Feitler, D.; Whitesides, G. M. Inorg. Chem. 1976, 15, 466-469. (b) Sekiya, A.; Stille, J. K. J. Am. Chem. Soc. 1981, 103, 5096-5100. (c) Koschinsky, R.; Kohli, T.-P.; Mayr, H. Tetrahedron Lett. 1988, 29, 5641-5644. (d) Lee, B. Y.; Moon, H.; Chung Y. K. J. Am. Chem. Soc. 1994, 116, 2163-2164. (e) Takahashi, T.; Xi, Z.; Kotora, M.; Xi, C. Tetrahedron Lett. 1996, 37, 7521-7524.
45. (a) Lee, G. C. M.; Tobias, B.; Holmes, J. M.; Harcourt, D. A.; Garst, M. E. J. Am. Chem. Soc. 1990, 112, 9330-9336.
46. (b) Silverberg, L. J.; Wu, G.; Rheingold, A. L.; Heck, R. F. J. Organomet. Chem. 1991, 409, 411-420.
47. (a) Hatanaka, M.; Himeda, Y.; Ueda, I. J. Chem. Soc., Perkin. Trans. 1 1993, 2269-2274.
48. (b) Hatanaka, M.; Himeda, Y.; Imashiro, R.; Tanaka, Y.; Ueda, I. J. Org. Chem. 1994, 59, 111-119.
49. (a) Bestmann, H. J. Angew. Chem., Int. Ed. Engl. 1965, 4, 583, 645, 830.
50. (b) Corey, E. J.; Erickson, B. W. J. Org. Chem. 1974, 39, 821-825.
51. (c) Bestmann, H. J.; Roth, K. Angew. Chem., Int. Ed. Engl. 1981, 20, 575-576.
52. (a) Büchi, G.; Wüest, H. Helv. Chim. Acta. 1971, 54, 1767-1776.
53. (b) Bohlmann, F.; Zdero, C. Chem. Ber. 1973, 106, 3779-3787.
54. (c) Dauben, W. G.; Ipaktschi, J. J. Am. Chem. Soc. 1973, 95, 5088-5089.
55. (d) Dauben, W. G.; Hart, D. J.; Ipaktschi, J.; Kozikowski, A. P. Tetrahedron Lett. 1973, 4425-4428.
56. (e) Dauben, W. G.; Kozikowski, A. P. Tetrahedron Lett. 1973, 3711-3714.
57. (f) Neff, J. R.; Gruetzmacher, R. R.; Nordlander, J. E. J. Org. Chem. 1974, 39, 3814-3819.
58. (g) Vedejs, E.; Bershas, J. P. Tetrahedron Lett. 1975, 1359-1362.
59. (h) Martin, S. F.; Desai, S. R. J. Org. Chem. 1977, 42, 1664-1666.
60. (i) Hatanaka, M.; Yamamoto, Y.; Ishimaru, T. J. Chem. Soc., Chem. Commun. 1984, 1705-1706.
61. For other annulations of allylidene(triphenyl)phosphorane, see: (a) Capuano, L.; Willmes, A. Liebigs Ann. Chem. 1982, 80-86. (b) Capuano, L.; Triesch, T.; Willmes, A. Chem. Ber. 1983, 116, 3767-3773. (c) Ipaktschi, J.; Saadatmandi, A. Liebigs Ann. Chem. 1984, 1989-1993. (d) Hatanaka, M.; Yamamoto, Y.; Ishimaru, T.; Takai, T. Chem. Lett. 1985, 183-186.
62. For other annulations of allylidene(triphenyl)phosphorane, see: (a) Capuano, L.; Willmes, A. Liebigs Ann. Chem. 1982, 80-86. (b) Capuano, L.; Triesch, T.; Willmes, A. Chem. Ber. 1983, 116, 3767-3773. (c) Ipaktschi, J.; Saadatmandi, A. Liebigs Ann. Chem. 1984, 1989-1993. (d) Hatanaka, M.; Yamamoto, Y.; Ishimaru, T.; Takai, T. Chem. Lett. 1985, 183-186.
63. For other annulations of allylidene(triphenyl)phosphorane, see: (a) Capuano, L.; Willmes, A. Liebigs Ann. Chem. 1982, 80-86. (b) Capuano, L.; Triesch, T.; Willmes, A. Chem. Ber. 1983, 116, 3767-3773. (c) Ipaktschi, J.; Saadatmandi, A. Liebigs Ann. Chem. 1984, 1989-1993. (d) Hatanaka, M.; Yamamoto, Y.; Ishimaru, T.; Takai, T. Chem. Lett. 1985, 183-186.
64. For other annulations of allylidene(triphenyl)phosphorane, see: (a) Capuano, L.; Willmes, A. Liebigs Ann. Chem. 1982, 80-86. (b) Capuano, L.; Triesch, T.; Willmes, A. Chem. Ber. 1983, 116, 3767-3773. (c) Ipaktschi, J.; Saadatmandi, A. Liebigs Ann. Chem. 1984, 1989-1993. (d) Hatanaka, M.; Yamamoto, Y.; Ishimaru, T.; Takai, T. Chem. Lett. 1985, 183-186.
65. (a) Barluenga, J.; Lopez, F.; Sanchez-Ferrando, F. Tetrahedron Lett. 1988, 29, 381-384.
66. (b) Johnson, A. W. Ylides and Imines of Phosphorus; John Wiley & Sons, Inc.: New York, 1993; pp 198-201.
67. (c) Weiyu, D.; Zang, P.; Cao, W. Tetrahedron Lett. 1987, 28, 81-82.
68. (d) Weiyu, D.; Weiguo, C.; Zhenrong, X.; Yuan, Y.; Zhijian, S.; Zhiheng, H. J. Chem. Soc., Perkin Trans. 1 1993, 855-858.
69. Preliminary report: Himeda, Y.; Hatanaka, M.; Ueda, I. J. Chem. Soc., Chem. Commun. 1995, 449-450. Himeda, Y.; Ueda, I.; Hatanaka, M. Chem. Lett. 1996, 71-72.
70. Preliminary report: Himeda, Y.; Hatanaka, M.; Ueda, I. J. Chem. Soc., Chem. Commun. 1995, 449-450. Himeda, Y.; Ueda, I.; Hatanaka, M. Chem. Lett. 1996, 71-72.
71. Compound 16d showed the peak (δ 6.61) due to the C-4 vinyl proton and the peaks (δ 3.53) due to the C-5 methylene protons, and in addition the NOESY spectrum revealed the cross peak between the C-4 vinyl proton (δ 6.61) and the C-3 phenyl protons. The COSY spectrum of 17d indicated the cross peaks between the C-5 methylene protons (δ 3.27) and the C-4 vinyl proton (δ 6.28) and between the former and the C-3 methyl protons (δ 1.92).
72. (a) McLean, S.; Hayes, P. Tetrahedron 1965, 21, 2313-2327, 2329-2342, 2343-2351.
73. (b) Spangler, C. W. Chem. Rev. 1976, 76, 187-217.
74. The sigmatropic migration occurred when 11a was heated in refluxing benzene for 3 h and led to the formation of a 2:1 mixture of 11a and 11b.
75. 1H NMR spectra that the isomeric dimer might be the endo isomer of 20: 3.40 (m, 1H, H-7), 2.86 (dd, J = 9.9, 18.0 Hz, 1H, H-5), 2.53 (bd, J = 18.0 Hz, 1H, H-5), 2.44 (dd, J = 1.8, 9.2 Hz, 1H, H-10), 2.01 (dd, J = 1.4, 9.2 Hz, 1H, H-10). However, a detailed examination was prevented by difficulty of purification and ready dissociation to the monomers in a solution.
76. For dimerization of cyclopentadienylcarboxylate, see: (a) Franklin, E.; Mack, C. H.; Rowland, S. P. J. Org. Chem. 1968, 33, 626-632. (b) Minter, D. E.; Marchand, A. P.; Lu, S.-p. Magn. Reson. Chem. 1990, 28, 623-627.
77. For dimerization of cyclopentadienylcarboxylate, see: (a) Franklin, E.; Mack, C. H.; Rowland, S. P. J. Org. Chem. 1968, 33, 626-632. (b) Minter, D. E.; Marchand, A. P.; Lu, S.-p. Magn. Reson. Chem. 1990, 28, 623-627.
78. The C-6 geometry was undoubtedly confirmed by the NOESY spectra; the cross peak between the C-6 proton and the C-4 methyl proton was observed for Z-28 but not for E-28.
79. For dimerization of fulvene, see: (a) Uebersax, B.; Neuenschwander, M.; Kellerhals, H.-P. Helv. Chim. Acta 1982, 65, 74-88.
80. (b) Uebersax, B.; Neuenshwander, M.; Engel, P. Helv. Chim. Acta 1982, 65, 89-104.
81. 2O solution. The isomerization also occurred at room temperature in an ether solution containing a weak base such as pyridine. It is likely that the extremely facile isomerization proceeds via an intermediary cyclopentadienyl anion produced by attack of a nucleophile at the 6-position.
82. Stewart, J. J. P. J. Comput. Chem. 1989, 10, 209-220, 221-264.
83. Frisch, M. J.; Trucks, G. W.; Head-Gordon, M.; Gill, P. M.; Wong, M. W.; Foresman, J. B.; Johnson, B. G.; Schlegel, H. B.; Robb, M. A.; Replogle, E. S.; Gomperts, R.; Andress, J. L.; Rachavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Pople, J. A. GAUSSIAN 92, Gaussian Inc., Pittsburgh, PA, 1992.
84. Mari, F.; Lahti, P. M.; McEwen, W. E. Heteroatom Chem. 1991, 2, 265-276. Mari, F.; Lahti, P. M.; McEwen, W. E. J. Am. Chem. Soc. 1992, 114, 813-821.
85. Mari, F.; Lahti, P. M.; McEwen, W. E. Heteroatom Chem. 1991, 2, 265-276. Mari, F.; Lahti, P. M.; McEwen, W. E. J. Am. Chem. Soc. 1992, 114, 813-821.
86. Vedejs, E.; Fleck, T. J. J. Am. Chem. Soc. 1989, 111, 5861-5871. Vedejs, E. Topics in Stereochemistry: Allinger, N. L., Eliel, E. L., Wilen, S. H., Eds; John Wiley & Sons, Inc.: New York, 1994; Vol. 21, pp 1-157.
87. Vedejs, E.; Fleck, T. J. J. Am. Chem. Soc. 1989, 111, 5861-5871. Vedejs, E. Topics in Stereochemistry: Allinger, N. L., Eliel, E. L., Wilen, S. H., Eds; John Wiley & Sons, Inc.: New York, 1994; Vol. 21, pp 1-157.
88. The several conformational isomers were each examined for pairs of the stereoisomers of TS1 and TS2, and the most stable transition states are depicted in Figure 1. The relative energies for the transition states and the oxaphosphetane stereoisomers that can be derived from those are listed in Scheme 6.