Effects of the π and π* orbitals of the 5-unsaturated substituents on the π-facial selectivities in the diels-alder reactions of cyclopentadienes

Chemistry Letters

Volumn , Issue 1, 1998, Pages 41-42

  Ishida, Masaru ^a   Kobayashi, Hiroki ^a   Tomohiro, Shingo ^a   Wasada, Hiroaki ^a   Inagaki, Satoshi ^a  

^a GIFU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0041125916     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.1998.41     Document Type: Article

References (21)

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7. Recent reports on π-facial selectivity in Diels-Alder reactions of 5-substituted cyclopentadienes: a) J. M. Coxon and D. Q. McDonald, Tetrahedron Lety., 33, 651 (1992).
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11. e) Review: A. G. Fallis and Y.-F. Lu, in "Advances in Cycloaddition" ed by D. P. Curran, JAI Press, Inc., Greenwich, CT(1993), Vol. 3, pp 1 and references cited therein.
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14. 5-Ethynylcyclopentadiene CpC≡CH is also expected to react at syn-face. Computation of the selectivity in the reactions of CpC≡N and CpC≡CH with ethylene was reported: See Ref. 3b.
15. W. Adam, U. Jacob, and M. Prein, J. Chem. Soc., Chem. Commun., 1995, 839.
16. Gaussian 94, Revision C.3, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, and J. A. Pople, Gaussian, Inc., Pittsburgh PA (1995).
17. 2 (-0.3794, 0.1861).
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19. The calculation of 1e gave similar results.
20. 2, J=17.5 and 11.5 Hz), 7.05-7.43 (m, 5H, Ph); 4f displayed an NOE between the methyl protons at δ 0.94 and the methyne protons at δ 3.12.
21. The importance of π-orbital participation is further supported by exclusive anti π-facial selectivity in the reaction of 5-ethyl-1,2,3,4,5-pentamethylcyclopentadiene: See Ref. 6.