A New and Selective Catalyst for the [5 + 2] Cycloaddition of Vinylcyclopropanes and Alkynes

Journal of Organic Chemistry

Volumn 63, Issue 13, 1998, Pages 4164-4165

  Wender, Paul A ^a   Sperandio, David ^a,b  

^a STANFORD UNIVERSITY   (United States)

^b Axys Pharmaceuticals Inc   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000625477     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9804240     Document Type: Article

References (30)

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16. Many transition metals have since been observed to react with strained C-C bonds. For a review, see: Crabtree, R. H. Chem. Rev. 1985, 85, 245-69.
17. For lead references, see: (a) Doyle, M. P.; Van Leusen, D. J. Org. Chem. 1982, 47, 5326-38. (b) Doyle, M. P.; Van Leusen, D. J. Am. Chem. Soc. 1981, 103, 5917-9. (c) Salomon, R. G.; Salomon, M. F.; Kachinski, J. L. C. J. Am. Chem. Soc. 1977, 99, 1043-54. (d) Voigt, H. W.; Roth, J. A. J. Catal. 1974, 33, 91-7. (e) Salomon, M. F.; Salomon, R. G. J. Chem. Soc., Chem. Commun. 1976, 3, 89-90. For transformations of vinyl cyclopropanes in the presence of Rh-, as well as Fe-, Co-, Ni-, and Pd-complexes, see: Khusnutdinov, R. I.; Dzhemilev, U. M. J. Organomet. Chem. 1994, 471, 1-18.
18. For lead references, see: (a) Doyle, M. P.; Van Leusen, D. J. Org. Chem. 1982, 47, 5326-38. (b) Doyle, M. P.; Van Leusen, D. J. Am. Chem. Soc. 1981, 103, 5917-9. (c) Salomon, R. G.; Salomon, M. F.; Kachinski, J. L. C. J. Am. Chem. Soc. 1977, 99, 1043-54. (d) Voigt, H. W.; Roth, J. A. J. Catal. 1974, 33, 91-7. (e) Salomon, M. F.; Salomon, R. G. J. Chem. Soc., Chem. Commun. 1976, 3, 89-90. For transformations of vinyl cyclopropanes in the presence of Rh-, as well as Fe-, Co-, Ni-, and Pd-complexes, see: Khusnutdinov, R. I.; Dzhemilev, U. M. J. Organomet. Chem. 1994, 471, 1-18.
19. For lead references, see: (a) Doyle, M. P.; Van Leusen, D. J. Org. Chem. 1982, 47, 5326-38. (b) Doyle, M. P.; Van Leusen, D. J. Am. Chem. Soc. 1981, 103, 5917-9. (c) Salomon, R. G.; Salomon, M. F.; Kachinski, J. L. C. J. Am. Chem. Soc. 1977, 99, 1043-54. (d) Voigt, H. W.; Roth, J. A. J. Catal. 1974, 33, 91-7. (e) Salomon, M. F.; Salomon, R. G. J. Chem. Soc., Chem. Commun. 1976, 3, 89-90. For transformations of vinyl cyclopropanes in the presence of Rh-, as well as Fe-, Co-, Ni-, and Pd-complexes, see: Khusnutdinov, R. I.; Dzhemilev, U. M. J. Organomet. Chem. 1994, 471, 1-18.
20. For lead references, see: (a) Doyle, M. P.; Van Leusen, D. J. Org. Chem. 1982, 47, 5326-38. (b) Doyle, M. P.; Van Leusen, D. J. Am. Chem. Soc. 1981, 103, 5917-9. (c) Salomon, R. G.; Salomon, M. F.; Kachinski, J. L. C. J. Am. Chem. Soc. 1977, 99, 1043-54. (d) Voigt, H. W.; Roth, J. A. J. Catal. 1974, 33, 91-7. (e) Salomon, M. F.; Salomon, R. G. J. Chem. Soc., Chem. Commun. 1976, 3, 89-90. For transformations of vinyl cyclopropanes in the presence of Rh-, as well as Fe-, Co-, Ni-, and Pd-complexes, see: Khusnutdinov, R. I.; Dzhemilev, U. M. J. Organomet. Chem. 1994, 471, 1-18.
21. For lead references, see: (a) Doyle, M. P.; Van Leusen, D. J. Org. Chem. 1982, 47, 5326-38. (b) Doyle, M. P.; Van Leusen, D. J. Am. Chem. Soc. 1981, 103, 5917-9. (c) Salomon, R. G.; Salomon, M. F.; Kachinski, J. L. C. J. Am. Chem. Soc. 1977, 99, 1043-54. (d) Voigt, H. W.; Roth, J. A. J. Catal. 1974, 33, 91-7. (e) Salomon, M. F.; Salomon, R. G. J. Chem. Soc., Chem. Commun. 1976, 3, 89-90. For transformations of vinyl cyclopropanes in the presence of Rh-, as well as Fe-, Co-, Ni-, and Pd-complexes, see: Khusnutdinov, R. I.; Dzhemilev, U. M. J. Organomet. Chem. 1994, 471, 1-18.
22. For lead references, see: (a) Doyle, M. P.; Van Leusen, D. J. Org. Chem. 1982, 47, 5326-38. (b) Doyle, M. P.; Van Leusen, D. J. Am. Chem. Soc. 1981, 103, 5917-9. (c) Salomon, R. G.; Salomon, M. F.; Kachinski, J. L. C. J. Am. Chem. Soc. 1977, 99, 1043-54. (d) Voigt, H. W.; Roth, J. A. J. Catal. 1974, 33, 91-7. (e) Salomon, M. F.; Salomon, R. G. J. Chem. Soc., Chem. Commun. 1976, 3, 89-90. For transformations of vinyl cyclopropanes in the presence of Rh-, as well as Fe-, Co-, Ni-, and Pd-complexes, see: Khusnutdinov, R. I.; Dzhemilev, U. M. J. Organomet. Chem. 1994, 471, 1-18.
23. Ryu, I.; Ikura, K.; Tamura, Y.; Maenaka, J.; Ogawa, A.; Sonoda, N. Synlett 1994, 941-2.
24. 2) or by GC (Wilkinson's catalyst).
25. Addition of the substrate over 3 h is required to keep the substrate concentration below 0.5 M. Substrate concentrations over 0.5 M reduce the rate of conversion.
26. 2 (5 mol %) was dissolved in toluene (4 mL) under a nitrogen atmosphere. Substrate 17 (0.2 mM) was added neat, and the resulting solution was heated at 110 °C for 20 min. After cooling, hexane was added (5 mL), and the reaction mixture was passed through silica gel (0.5 g). The product was eluted with hexane/AcOEt = 20/1. Concentration in vacuo gives 18 in 82% as a colorless oil.
27. Studies of Lehmkuhl showed that coordinatively unsaturated (cycloalkylmethyl)bis(cyclopentadienyl)titanium and nickel complexes rear-range by ring opening: (a) Lehmkuhl, H.; Rufinska, A.; Benn, R.; Schroth, G.; Mynott, R. Liebigs Ann. Chem. 1981, 317-32. (b) Lehmkuhl, H.; Fustero, S. Liebigs Ann. Chem. 1980, 1361-70. For an excellent rewiew about organometallic derivatives of cyclopropanes and their reactions, see: Goldschmidt, Z. In The chemistry of the cydopropyl group; Rappoport, Z., Ed.; John Wiley: London. 1995; Vol 2; pp 498-647. For a theoretical study of the activation of C-C bonds by transition-metal atoms, see: Siegbahn, E. M.; Blomberg, M. R. A. J. Am. Chem. Soc. 1992, 114, 10548-56.
28. Studies of Lehmkuhl showed that coordinatively unsaturated (cycloalkylmethyl)bis(cyclopentadienyl)titanium and nickel complexes rear-range by ring opening: (a) Lehmkuhl, H.; Rufinska, A.; Benn, R.; Schroth, G.; Mynott, R. Liebigs Ann. Chem. 1981, 317-32. (b) Lehmkuhl, H.; Fustero, S. Liebigs Ann. Chem. 1980, 1361-70. For an excellent rewiew about organometallic derivatives of cyclopropanes and their reactions, see: Goldschmidt, Z. In The chemistry of the cydopropyl group; Rappoport, Z., Ed.; John Wiley: London. 1995; Vol 2; pp 498-647. For a theoretical study of the activation of C-C bonds by transition-metal atoms, see: Siegbahn, E. M.; Blomberg, M. R. A. J. Am. Chem. Soc. 1992, 114, 10548-56.
29. Studies of Lehmkuhl showed that coordinatively unsaturated (cycloalkylmethyl)bis(cyclopentadienyl)titanium and nickel complexes rear-range by ring opening: (a) Lehmkuhl, H.; Rufinska, A.; Benn, R.; Schroth, G.; Mynott, R. Liebigs Ann. Chem. 1981, 317-32. (b) Lehmkuhl, H.; Fustero, S. Liebigs Ann. Chem. 1980, 1361-70. For an excellent rewiew about organometallic derivatives of cyclopropanes and their reactions, see: Goldschmidt, Z. In The chemistry of the cydopropyl group; Rappoport, Z., Ed.; John Wiley: London. 1995; Vol 2; pp 498-647. For a theoretical study of the activation of C-C bonds by transition-metal atoms, see: Siegbahn, E. M.; Blomberg, M. R. A. J. Am. Chem. Soc. 1992, 114, 10548-56.
30. Studies of Lehmkuhl showed that coordinatively unsaturated (cycloalkylmethyl)bis(cyclopentadienyl)titanium and nickel complexes rear-range by ring opening: (a) Lehmkuhl, H.; Rufinska, A.; Benn, R.; Schroth, G.; Mynott, R. Liebigs Ann. Chem. 1981, 317-32. (b) Lehmkuhl, H.; Fustero, S. Liebigs Ann. Chem. 1980, 1361-70. For an excellent rewiew about organometallic derivatives of cyclopropanes and their reactions, see: Goldschmidt, Z. In The chemistry of the cydopropyl group; Rappoport, Z., Ed.; John Wiley: London. 1995; Vol 2; pp 498-647. For a theoretical study of the activation of C-C bonds by transition-metal atoms, see: Siegbahn, E. M.; Blomberg, M. R. A. J. Am. Chem. Soc. 1992, 114, 10548-56.