Structural effects affecting the thermal electrocyclic ring closure of vinylallenes to alkylidenecyclobutenes

Journal of the American Chemical Society

Volumn 118, Issue 8, 1996, Pages 1881-1891

  López, Susana ^a   Rodríguez, Jesús ^a   Rey, José García ^a   De Lera, Angel R ^a  

^a UNIVERSITY OF SANTIAGO DE COMPOSTELA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOBUTANE DERIVATIVE; CYCLOBUTENE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; DRUG SYNTHESIS; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS;

EID: 0029947240     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9522241     Document Type: Article

References (60)

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18. For leading references on the chemistry of vinylallenes, see: (a) Okamura, W. H. Acc. Chem. Res. 1983, 16, 81. (b) Pasto, D. J. Tetrahedron 1984, 40, 2805. (c) Okamura, W. H.; Curtin, M. L. Synlett 1990, 1. For monographs, see: (d) The Chemistry of Ketenes, Allenes and Related Compounds, Part I and Part II; Patai, S., Ed.; John Wiley and Sons: New York, 1980. (e) Landor, S. R. The Chemistry of the Allenes: Academic Press: New York, 1982. (f) Schuster, H. F.; Coppola, G. M. Allenes in Organic Chemistry; Wiley: New York. 1984.
19. For leading references on the chemistry of vinylallenes, see: (a) Okamura, W. H. Acc. Chem. Res. 1983, 16, 81. (b) Pasto, D. J. Tetrahedron 1984, 40, 2805. (c) Okamura, W. H.; Curtin, M. L. Synlett 1990, 1. For monographs, see: (d) The Chemistry of Ketenes, Allenes and Related Compounds, Part I and Part II; Patai, S., Ed.; John Wiley and Sons: New York, 1980. (e) Landor, S. R. The Chemistry of the Allenes: Academic Press: New York, 1982. (f) Schuster, H. F.; Coppola, G. M. Allenes in Organic Chemistry; Wiley: New York. 1984.
20. For leading references on the chemistry of vinylallenes, see: (a) Okamura, W. H. Acc. Chem. Res. 1983, 16, 81. (b) Pasto, D. J. Tetrahedron 1984, 40, 2805. (c) Okamura, W. H.; Curtin, M. L. Synlett 1990, 1. For monographs, see: (d) The Chemistry of Ketenes, Allenes and Related Compounds, Part I and Part II; Patai, S., Ed.; John Wiley and Sons: New York, 1980. (e) Landor, S. R. The Chemistry of the Allenes: Academic Press: New York, 1982. (f) Schuster, H. F.; Coppola, G. M. Allenes in Organic Chemistry; Wiley: New York. 1984.
21. For leading references on the chemistry of vinylallenes, see: (a) Okamura, W. H. Acc. Chem. Res. 1983, 16, 81. (b) Pasto, D. J. Tetrahedron 1984, 40, 2805. (c) Okamura, W. H.; Curtin, M. L. Synlett 1990, 1. For monographs, see: (d) The Chemistry of Ketenes, Allenes and Related Compounds, Part I and Part II; Patai, S., Ed.; John Wiley and Sons: New York, 1980. (e) Landor, S. R. The Chemistry of the Allenes: Academic Press: New York, 1982. (f) Schuster, H. F.; Coppola, G. M. Allenes in Organic Chemistry; Wiley: New York. 1984.
22. For leading references on the chemistry of vinylallenes, see: (a) Okamura, W. H. Acc. Chem. Res. 1983, 16, 81. (b) Pasto, D. J. Tetrahedron 1984, 40, 2805. (c) Okamura, W. H.; Curtin, M. L. Synlett 1990, 1. For monographs, see: (d) The Chemistry of Ketenes, Allenes and Related Compounds, Part I and Part II; Patai, S., Ed.; John Wiley and Sons: New York, 1980. (e) Landor, S. R. The Chemistry of the Allenes: Academic Press: New York, 1982. (f) Schuster, H. F.; Coppola, G. M. Allenes in Organic Chemistry; Wiley: New York. 1984.
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28. (a) Upon heating to 170 °C, the parent penta-1,2,4-triene gives, among other dimeric products, the parent methylenecyclobutene. See: Schneider, R.; Siegel, H.; Hopf, H. Liebigs Ann. Chem. 1981, 1812. We thank Prof. Hopf for calling our attention to some of his early ideas on periselectivity in vinylallenes: Hopf, H. Nachr. Chem. Techn. 1975, 23, 235 .
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44. 2 center (outward-inward) for the conrotatory mode leading to the (E)-alkylidenecyclobutenes.
45. 6 and evaporation of deuterated solvent resulted in complete loss of product. Characterization was therefore based on the comparison of available NMR data with relevant data for E-30a and Z-30a.
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58. 4b at the transition state has been calculated for two of the representative divinylallenes, 46 and 48. It is greater for the latter and for the transition structures leading to the Z isomers: 46 - E-47, 54%: 46 - Z-47, 56%: 48 - E-49, 56%: 48 - Z-49, 59%. The geometric parameters of the vinylallenes 46 and 48 and the alkylidenecyclobutenes E-47, Z-47, E-49, and Z-49 can be found in the supporting information.
59. 13C NMR analysis before mass spectral determinations. As evidence of purity. NMR spectra are included in the supporting information.
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