Ruthenium-catalyzed aromatization of enediynes via highly regioselective nucleophilic additions on a π-alkyne functionality. A useful method for the synthesis of functionalized benzene derivatives

Journal of the American Chemical Society

Volumn 127, Issue 10, 2005, Pages 3406-3412

  Odedra, Arjan ^a   Wu, Chang Jung ^a   Pratap, Taduri Bhanu ^a   Huang, Chun Wei ^a   Ran, Ying Fen ^a   Liu, Rai Shung ^a  

^a NATIONAL TSING HUA UNIVERSITY   (Taiwan)

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; BENZENE; CATALYSIS; FUNCTIONAL POLYMERS; ISOMERS; POSITIVE IONS; RUTHENIUM; SUBSTITUTION REACTIONS;

ALKYNES; CYCLIZATION; DIMETHYL MALONATE; PYRROLES;

ORGANIC COMPOUNDS;

ACETYLACETONE; ALCOHOL; ALKYNE; ANILINE; BENZENE DERIVATIVE; CATION; DEUTERIUM; MALONIC ACID; NAPHTHALENE; PYRROLE; RUTHENIUM; WATER;

AROMATIZATION; ARTICLE; CATALYSIS; CHEMICAL REACTION; CYCLIZATION; ISOMER; MOLECULAR WEIGHT; SYNTHESIS;

EID: 14944386614     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja043047j     Document Type: Article

References (67)

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24. For the cyclization of strained enediynes with anionic nucleophiles, the enediynes actually underwent traditional Bergman or Saito-Myers diradical processes after attack of anionic nucleophiles. For examples, see: (a) Nicolaou, K. C.; Dai, W. M. Angew. Chem., Int. Ed. Engl. 1991, 30, 1387 and references therein. (b) Hirama, M.; Fujiwara, K.; Shigematsu, K.; Fukazara, Y. J. Am. Chem. Soc. 1989, 111, 4120. (c) Wender, P. A.; Hartmata, M.; Jefferey, D.; Mukai, C.; Suffert, J. Tetrahedron Lett. 1988, 29, 909. (d) Bekele, T.; Brunette, S. R.; Lipton, M. A. J. Org. Chem. 2003, 68, 8741.
25. For the cyclization of strained enediynes with anionic nucleophiles, the enediynes actually underwent traditional Bergman or Saito-Myers diradical processes after attack of anionic nucleophiles. For examples, see: (a) Nicolaou, K. C.; Dai, W. M. Angew. Chem., Int. Ed. Engl. 1991, 30, 1387 and references therein. (b) Hirama, M.; Fujiwara, K.; Shigematsu, K.; Fukazara, Y. J. Am. Chem. Soc. 1989, 111, 4120. (c) Wender, P. A.; Hartmata, M.; Jefferey, D.; Mukai, C.; Suffert, J. Tetrahedron Lett. 1988, 29, 909. (d) Bekele, T.; Brunette, S. R.; Lipton, M. A. J. Org. Chem. 2003, 68, 8741.
26. For the cyclization of strained enediynes with anionic nucleophiles, the enediynes actually underwent traditional Bergman or Saito-Myers diradical processes after attack of anionic nucleophiles. For examples, see: (a) Nicolaou, K. C.; Dai, W. M. Angew. Chem., Int. Ed. Engl. 1991, 30, 1387 and references therein. (b) Hirama, M.; Fujiwara, K.; Shigematsu, K.; Fukazara, Y. J. Am. Chem. Soc. 1989, 111, 4120. (c) Wender, P. A.; Hartmata, M.; Jefferey, D.; Mukai, C.; Suffert, J. Tetrahedron Lett. 1988, 29, 909. (d) Bekele, T.; Brunette, S. R.; Lipton, M. A. J. Org. Chem. 2003, 68, 8741.
27. For the cyclization of strained enediynes with anionic nucleophiles, the enediynes actually underwent traditional Bergman or Saito-Myers diradical processes after attack of anionic nucleophiles. For examples, see: (a) Nicolaou, K. C.; Dai, W. M. Angew. Chem., Int. Ed. Engl. 1991, 30, 1387 and references therein. (b) Hirama, M.; Fujiwara, K.; Shigematsu, K.; Fukazara, Y. J. Am. Chem. Soc. 1989, 111, 4120. (c) Wender, P. A.; Hartmata, M.; Jefferey, D.; Mukai, C.; Suffert, J. Tetrahedron Lett. 1988, 29, 909. (d) Bekele, T.; Brunette, S. R.; Lipton, M. A. J. Org. Chem. 2003, 68, 8741.
28. For cyclization of enediynes via diradical pathways, see: ref 1b and (a) Jones, L. H.; Hartwig, C. W.; Wentworth, P., Jr.; Simeonov, A.; Wentworth, A. D.; Py, S.; Ashley, J. A.; Lerner, R. A.; Janda, K. D. J. Am. Chem. Soc. 2001, 123, 3607. (b) Grissom, J. W.; Gunawardena, G. U. Tetrahedron Lett. 1995 36, 4951. (c) Schottelius, M.; Chen, P. J. Am. Chem. Soc. 1996, 118, 4896. (d) Dai, W.-M. Curr. Med. Chem. 2003, 10, 2265.
29. For cyclization of enediynes via diradical pathways, see: ref 1b and (a) Jones, L. H.; Hartwig, C. W.; Wentworth, P., Jr.; Simeonov, A.; Wentworth, A. D.; Py, S.; Ashley, J. A.; Lerner, R. A.; Janda, K. D. J. Am. Chem. Soc. 2001, 123, 3607. (b) Grissom, J. W.; Gunawardena, G. U. Tetrahedron Lett. 1995 36, 4951. (c) Schottelius, M.; Chen, P. J. Am. Chem. Soc. 1996, 118, 4896. (d) Dai, W.-M. Curr. Med. Chem. 2003, 10, 2265.
30. For cyclization of enediynes via diradical pathways, see: ref 1b and (a) Jones, L. H.; Hartwig, C. W.; Wentworth, P., Jr.; Simeonov, A.; Wentworth, A. D.; Py, S.; Ashley, J. A.; Lerner, R. A.; Janda, K. D. J. Am. Chem. Soc. 2001, 123, 3607. (b) Grissom, J. W.; Gunawardena, G. U. Tetrahedron Lett. 1995 36, 4951. (c) Schottelius, M.; Chen, P. J. Am. Chem. Soc. 1996, 118, 4896. (d) Dai, W.-M. Curr. Med. Chem. 2003, 10, 2265.
31. For cyclization of enediynes via diradical pathways, see: ref 1b and (a) Jones, L. H.; Hartwig, C. W.; Wentworth, P., Jr.; Simeonov, A.; Wentworth, A. D.; Py, S.; Ashley, J. A.; Lerner, R. A.; Janda, K. D. J. Am. Chem. Soc. 2001, 123, 3607. (b) Grissom, J. W.; Gunawardena, G. U. Tetrahedron Lett. 1995 36, 4951. (c) Schottelius, M.; Chen, P. J. Am. Chem. Soc. 1996, 118, 4896. (d) Dai, W.-M. Curr. Med. Chem. 2003, 10, 2265.
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36. For catalytic reactions that use this ruthenium catalyst, see the following selected examples: (a) Yeh, K.-L.; Liu, B.; Lo, C.-Y.; Liu, R.-S. J. Am. Chem. Soc. 2002, 124, 6510. (b) Datta, S.; Chang, C.-L.; Yeh, K.-L.; Liu, R.-S. J. Am. Chem. Soc. 2003, 125, 9294. (c) Shen, H.-C.; Pal, S.; Lian, J.-J.; Liu, R.-S. J. Am. Chem. Soc. 2003, 125, 15762. (d) Madhushaw, R. J.; Lin, M.-Y.; Abu Sohel, S. M.; Liu, R.-S. J. Am. Chem. Soc. 2004, 126, 6895. (e) Madhushaw, R.-J.; Lo, C.-Y.; Huang, C.-W.; Su, M.-D.; Shen, H.-C.; Pal, S.; Shaikh, I. R.; Liu, R.-S. J. Am. Chem. Soc. 2004, 126, 15560.
37. For catalytic reactions that use this ruthenium catalyst, see the following selected examples: (a) Yeh, K.-L.; Liu, B.; Lo, C.-Y.; Liu, R.-S. J. Am. Chem. Soc. 2002, 124, 6510. (b) Datta, S.; Chang, C.-L.; Yeh, K.-L.; Liu, R.-S. J. Am. Chem. Soc. 2003, 125, 9294. (c) Shen, H.-C.; Pal, S.; Lian, J.-J.; Liu, R.-S. J. Am. Chem. Soc. 2003, 125, 15762. (d) Madhushaw, R. J.; Lin, M.-Y.; Abu Sohel, S. M.; Liu, R.-S. J. Am. Chem. Soc. 2004, 126, 6895. (e) Madhushaw, R.-J.; Lo, C.-Y.; Huang, C.-W.; Su, M.-D.; Shen, H.-C.; Pal, S.; Shaikh, I. R.; Liu, R.-S. J. Am. Chem. Soc. 2004, 126, 15560.
38. For catalytic reactions that use this ruthenium catalyst, see the following selected examples: (a) Yeh, K.-L.; Liu, B.; Lo, C.-Y.; Liu, R.-S. J. Am. Chem. Soc. 2002, 124, 6510. (b) Datta, S.; Chang, C.-L.; Yeh, K.-L.; Liu, R.-S. J. Am. Chem. Soc. 2003, 125, 9294. (c) Shen, H.-C.; Pal, S.; Lian, J.-J.; Liu, R.-S. J. Am. Chem. Soc. 2003, 125, 15762. (d) Madhushaw, R. J.; Lin, M.-Y.; Abu Sohel, S. M.; Liu, R.-S. J. Am. Chem. Soc. 2004, 126, 6895. (e) Madhushaw, R.-J.; Lo, C.-Y.; Huang, C.-W.; Su, M.-D.; Shen, H.-C.; Pal, S.; Shaikh, I. R.; Liu, R.-S. J. Am. Chem. Soc. 2004, 126, 15560.
39. For catalytic reactions that use this ruthenium catalyst, see the following selected examples: (a) Yeh, K.-L.; Liu, B.; Lo, C.-Y.; Liu, R.-S. J. Am. Chem. Soc. 2002, 124, 6510. (b) Datta, S.; Chang, C.-L.; Yeh, K.-L.; Liu, R.-S. J. Am. Chem. Soc. 2003, 125, 9294. (c) Shen, H.-C.; Pal, S.; Lian, J.-J.; Liu, R.-S. J. Am. Chem. Soc. 2003, 125, 15762. (d) Madhushaw, R. J.; Lin, M.-Y.; Abu Sohel, S. M.; Liu, R.-S. J. Am. Chem. Soc. 2004, 126, 6895. (e) Madhushaw, R.-J.; Lo, C.-Y.; Huang, C.-W.; Su, M.-D.; Shen, H.-C.; Pal, S.; Shaikh, I. R.; Liu, R.-S. J. Am. Chem. Soc. 2004, 126, 15560.
40. For catalytic reactions that use this ruthenium catalyst, see the following selected examples: (a) Yeh, K.-L.; Liu, B.; Lo, C.-Y.; Liu, R.-S. J. Am. Chem. Soc. 2002, 124, 6510. (b) Datta, S.; Chang, C.-L.; Yeh, K.-L.; Liu, R.-S. J. Am. Chem. Soc. 2003, 125, 9294. (c) Shen, H.-C.; Pal, S.; Lian, J.-J.; Liu, R.-S. J. Am. Chem. Soc. 2003, 125, 15762. (d) Madhushaw, R. J.; Lin, M.-Y.; Abu Sohel, S. M.; Liu, R.-S. J. Am. Chem. Soc. 2004, 126, 6895. (e) Madhushaw, R.-J.; Lo, C.-Y.; Huang, C.-W.; Su, M.-D.; Shen, H.-C.; Pal, S.; Shaikh, I. R.; Liu, R.-S. J. Am. Chem. Soc. 2004, 126, 15560.
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45. In the presence of aliphatic amine base, cationic ruthenium complex tends to react with terminal alkyne to give alkynyl ruthenium species. See: (a) Bustelo, E.; Carbo, J. J.; Lledos, A.; Mereiter, K.; Puerta, M. C.; Valerga, P. J. Am. Chem. Soc. 2003, 125, 3311. (b) Bruce, M. I.; Wallis, R. C. Aust. J. Chem. 1979, 32, 1471. (c) Haquette, D. T.; Pirio, N.; Touchard, L.; Toupet, P. H.; Dixneuf, J. J. Chem. Soc., Chem. Commun. 1993, 163. (d) Yang, S.-M.; Chan, M. C.-W.; Cheung, K.-K.; Che, C.-M.; Peng, S.-M. Organometallics 1997, 16, 2819.
46. In the presence of aliphatic amine base, cationic ruthenium complex tends to react with terminal alkyne to give alkynyl ruthenium species. See: (a) Bustelo, E.; Carbo, J. J.; Lledos, A.; Mereiter, K.; Puerta, M. C.; Valerga, P. J. Am. Chem. Soc. 2003, 125, 3311. (b) Bruce, M. I.; Wallis, R. C. Aust. J. Chem. 1979, 32, 1471. (c) Haquette, D. T.; Pirio, N.; Touchard, L.; Toupet, P. H.; Dixneuf, J. J. Chem. Soc., Chem. Commun. 1993, 163. (d) Yang, S.-M.; Chan, M. C.-W.; Cheung, K.-K.; Che, C.-M.; Peng, S.-M. Organometallics 1997, 16, 2819.
47. In the presence of aliphatic amine base, cationic ruthenium complex tends to react with terminal alkyne to give alkynyl ruthenium species. See: (a) Bustelo, E.; Carbo, J. J.; Lledos, A.; Mereiter, K.; Puerta, M. C.; Valerga, P. J. Am. Chem. Soc. 2003, 125, 3311. (b) Bruce, M. I.; Wallis, R. C. Aust. J. Chem. 1979, 32, 1471. (c) Haquette, D. T.; Pirio, N.; Touchard, L.; Toupet, P. H.; Dixneuf, J. J. Chem. Soc., Chem. Commun. 1993, 163. (d) Yang, S.-M.; Chan, M. C.-W.; Cheung, K.-K.; Che, C.-M.; Peng, S.-M. Organometallics 1997, 16, 2819.
48. In the presence of aliphatic amine base, cationic ruthenium complex tends to react with terminal alkyne to give alkynyl ruthenium species. See: (a) Bustelo, E.; Carbo, J. J.; Lledos, A.; Mereiter, K.; Puerta, M. C.; Valerga, P. J. Am. Chem. Soc. 2003, 125, 3311. (b) Bruce, M. I.; Wallis, R. C. Aust. J. Chem. 1979, 32, 1471. (c) Haquette, D. T.; Pirio, N.; Touchard, L.; Toupet, P. H.; Dixneuf, J. J. Chem. Soc., Chem. Commun. 1993, 163. (d) Yang, S.-M.; Chan, M. C.-W.; Cheung, K.-K.; Che, C.-M.; Peng, S.-M. Organometallics 1997, 16, 2819.
49. (a) Mizushima, E.; Sato, K.; Hayashi, T.; Tanaka, M. Angew. Chem., Int. Ed. Engl. 2002, 41, 4563.
50. (b) Tokunaga, M.; Wakatsuki, Y. Angew. Chem., Int. Ed. Engl. 1998, 37, 2867.
51. (c) Damiano, J. P.; Postel, M. J. Organomet. Chem. 1996, 522, 303.
52. (d) Uemura, S.; Miyoshi, H.; Okano, M. J. Chem. Soc., Perkin Trans. 1 1980, 1098.
53. (e) Baidossi, W.; Lahav, M.; Blum, J. J. Org. Chem. 1997, 62, 669.
54. The structures of the addition products in Tables 1-4 were assigned on the basis of two new doublets (J = 7.8-8.0 Hz) in the aromatic regions.
55. 6 with an equimolar amount of phosphine ligand.
56. nBu) was transferred equally to the C(3) and C(4) carbons of the cyclopentyl product 6b. (Chemical Equation Presented)
57. 3SiH will add to carbene intermediate via a Si-H bond insertion. See: (a) Alder, R. W. In Carbene Chemistry; Bertrand, G., Ed.; Marcel Dekker: New York, 2002; p 153.
58. (b) Bertrand G. In Carbene Chemistry; Bertrand, G., Ed.; Marcel Dekker: New York, 2002; pp 177-203.
59. 6 (3-pentanone, 100°C, 72 h) and HCl (aq, 2.0 equiv). Under this condition, unreacted enediyne 1j was only recovered in 15% with formation of a black heavy oil. This information suggests that this catalytic reaction is slower than the decomposition of enediynes 1j by ruthenium catalyst alone.
60. 2O and alkynyl proton can proceed via an alkynyl ruthenium hydride species, which was responsible for the ruthenium-π-alkyne and ruthenium-vinylidene equilibrium. See refs 12 and 16.
61. Miura, T.; Iwasawa, N. J. Am. Chem. Soc. 2002, 124, 518.
62. 1H NOE map of naphthalenes 11a and 11b is shown in the Supporting Information.
63. For a mechanistic study of the cis-vinylmetal and trans-vinylmetal isomerization reaction, see: Bodner, G. S.; Smith, D. E.; Hatton, W. G.; Heah, P. C.; Georgiou, S.; Reingold, A. L.; Geib, S. J.; Hutchinson, J. P.; Gladysz, J. A. J. Am. Chem. Soc. 1987, 109, 7688.
64. For the trans-insertion of alkyne into metal-hydride and -chloride bonds, see: (a) Huggins, J. M.; Bergman, R. G. J. Am. Chem. Soc. 1981, 103, 3002. (b) Vessey, J. D.; Mawby, R. J. J. Chem. Soc., Dalton Trans. 1993, 51.
65. For the trans-insertion of alkyne into metal-hydride and -chloride bonds, see: (a) Huggins, J. M.; Bergman, R. G. J. Am. Chem. Soc. 1981, 103, 3002. (b) Vessey, J. D.; Mawby, R. J. J. Chem. Soc., Dalton Trans. 1993, 51.
66. 3 fragment to destabilize this species in accordance with our proposal in the text. This observation strengthens our views about the steric effects of enediynes on the catalytic activity.
67. 2 gives additional support for the proposed π-alkyne intermediate.