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( 6) For intramolecular hetero-Michael additions used in the synthesis of tetrahydropyrans, see: (a) Maurer, B.; Grieder, A.; Thommen, W. Helv. Chim. Acta 1979, 62, 44. (b) Seebach, D.; Pohmakotr, M. Helv. Chim. Acta 1979, 62, 843. (c) Kozikowski, A. P.; Schmiesing, R. J.; Sorgi, K. L. J. Am. Chem. Soc. 1980, 102, 6577. (d) Bates, H. A.; Deng, P.-N. J. Org. Chem. 1983, 48, 4479. (e) Crimmins, M. T.; O'Mahony, R. J. Org. Chem. 1989, 54, 1157. (f) Allevi, P.; Ciuffreda, P.; Colombo, D.; Monti, D.; Speranza, G.; Manitto, P. J. Chem. Soc., Perkin Trans. 1, 1989, 1281. (g) Kim, S.; Salomon, R. G. Tetrahedron Lett. 1989, 30, 6279. (h) Nicolaou, K. C.; Hwang, C.-K.; Duggan, M. E. J. Am. Chem. Soc. 1989, 111, 6682. (i). Hori, K.; Hikage, N.; Inagaki, A.; Mori, S.; Nomura, K.; Yoshii, E. J. Org. Chem. 1992, 57, 2888. (j) Aicher, T. D.; Buszek, K. R.; Fang, F. G.; Forsyth, C. J.; Jung, S. H.; Kishi, Y.; Scola, P. M. Tetrahedron Lett. 1992, 33, 1549. (k) Machinaga, N.; Kibayashi, C. Tetrahedron Lett. 1993, 34, 5739. (1) Dheilly, L.; Lièvre, C.; Fréehou, C.; Demailly, G. Tetrahedron Lett. 1993, 34, 5895. (m) Horita, K.; Hachiya, S.; Nagasawa, M., Hikota, M.; Yonemitsu, O. Synlett 1994, 38. (n) Roedern, E. G.; Kessler, H. Angew. Chem., Int. Ed. Engl. 1994, 33, 687.
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0027218163
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( 6) For intramolecular hetero-Michael additions used in the synthesis of tetrahydropyrans, see: (a) Maurer, B.; Grieder, A.; Thommen, W. Helv. Chim. Acta 1979, 62, 44. (b) Seebach, D.; Pohmakotr, M. Helv. Chim. Acta 1979, 62, 843. (c) Kozikowski, A. P.; Schmiesing, R. J.; Sorgi, K. L. J. Am. Chem. Soc. 1980, 102, 6577. (d) Bates, H. A.; Deng, P.-N. J. Org. Chem. 1983, 48, 4479. (e) Crimmins, M. T.; O'Mahony, R. J. Org. Chem. 1989, 54, 1157. (f) Allevi, P.; Ciuffreda, P.; Colombo, D.; Monti, D.; Speranza, G.; Manitto, P. J. Chem. Soc., Perkin Trans. 1, 1989, 1281. (g) Kim, S.; Salomon, R. G. Tetrahedron Lett. 1989, 30, 6279. (h) Nicolaou, K. C.; Hwang, C.-K.; Duggan, M. E. J. Am. Chem. Soc. 1989, 111, 6682. (i). Hori, K.; Hikage, N.; Inagaki, A.; Mori, S.; Nomura, K.; Yoshii, E. J. Org. Chem. 1992, 57, 2888. (j) Aicher, T. D.; Buszek, K. R.; Fang, F. G.; Forsyth, C. J.; Jung, S. H.; Kishi, Y.; Scola, P. M. Tetrahedron Lett. 1992, 33, 1549. (k) Machinaga, N.; Kibayashi, C. Tetrahedron Lett. 1993, 34, 5739. (1) Dheilly, L.; Lièvre, C.; Fréehou, C.; Demailly, G. Tetrahedron Lett. 1993, 34, 5895. (m) Horita, K.; Hachiya, S.; Nagasawa, M., Hikota, M.; Yonemitsu, O. Synlett 1994, 38. (n) Roedern, E. G.; Kessler, H. Angew. Chem., Int. Ed. Engl. 1994, 33, 687.
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( 6) For intramolecular hetero-Michael additions used in the synthesis of tetrahydropyrans, see: (a) Maurer, B.; Grieder, A.; Thommen, W. Helv. Chim. Acta 1979, 62, 44. (b) Seebach, D.; Pohmakotr, M. Helv. Chim. Acta 1979, 62, 843. (c) Kozikowski, A. P.; Schmiesing, R. J.; Sorgi, K. L. J. Am. Chem. Soc. 1980, 102, 6577. (d) Bates, H. A.; Deng, P.-N. J. Org. Chem. 1983, 48, 4479. (e) Crimmins, M. T.; O'Mahony, R. J. Org. Chem. 1989, 54, 1157. (f) Allevi, P.; Ciuffreda, P.; Colombo, D.; Monti, D.; Speranza, G.; Manitto, P. J. Chem. Soc., Perkin Trans. 1, 1989, 1281. (g) Kim, S.; Salomon, R. G. Tetrahedron Lett. 1989, 30, 6279. (h) Nicolaou, K. C.; Hwang, C.-K.; Duggan, M. E. J. Am. Chem. Soc. 1989, 111, 6682. (i). Hori, K.; Hikage, N.; Inagaki, A.; Mori, S.; Nomura, K.; Yoshii, E. J. Org. Chem. 1992, 57, 2888. (j) Aicher, T. D.; Buszek, K. R.; Fang, F. G.; Forsyth, C. J.; Jung, S. H.; Kishi, Y.; Scola, P. M. Tetrahedron Lett. 1992, 33, 1549. (k) Machinaga, N.; Kibayashi, C. Tetrahedron Lett. 1993, 34, 5739. (1) Dheilly, L.; Lièvre, C.; Fréehou, C.; Demailly, G. Tetrahedron Lett. 1993, 34, 5895. (m) Horita, K.; Hachiya, S.; Nagasawa, M., Hikota, M.; Yonemitsu, O. Synlett 1994, 38. (n) Roedern, E. G.; Kessler, H. Angew. Chem., Int. Ed. Engl. 1994, 33, 687.
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( 6) For intramolecular hetero-Michael additions used in the synthesis of tetrahydropyrans, see: (a) Maurer, B.; Grieder, A.; Thommen, W. Helv. Chim. Acta 1979, 62, 44. (b) Seebach, D.; Pohmakotr, M. Helv. Chim. Acta 1979, 62, 843. (c) Kozikowski, A. P.; Schmiesing, R. J.; Sorgi, K. L. J. Am. Chem. Soc. 1980, 102, 6577. (d) Bates, H. A.; Deng, P.-N. J. Org. Chem. 1983, 48, 4479. (e) Crimmins, M. T.; O'Mahony, R. J. Org. Chem. 1989, 54, 1157. (f) Allevi, P.; Ciuffreda, P.; Colombo, D.; Monti, D.; Speranza, G.; Manitto, P. J. Chem. Soc., Perkin Trans. 1, 1989, 1281. (g) Kim, S.; Salomon, R. G. Tetrahedron Lett. 1989, 30, 6279. (h) Nicolaou, K. C.; Hwang, C.-K.; Duggan, M. E. J. Am. Chem. Soc. 1989, 111, 6682. (i). Hori, K.; Hikage, N.; Inagaki, A.; Mori, S.; Nomura, K.; Yoshii, E. J. Org. Chem. 1992, 57, 2888. (j) Aicher, T. D.; Buszek, K. R.; Fang, F. G.; Forsyth, C. J.; Jung, S. H.; Kishi, Y.; Scola, P. M. Tetrahedron Lett. 1992, 33, 1549. (k) Machinaga, N.; Kibayashi, C. Tetrahedron Lett. 1993, 34, 5739. (1) Dheilly, L.; Lièvre, C.; Fréehou, C.; Demailly, G. Tetrahedron Lett. 1993, 34, 5895. (m) Horita, K.; Hachiya, S.; Nagasawa, M., Hikota, M.; Yonemitsu, O. Synlett 1994, 38. (n) Roedern, E. G.; Kessler, H. Angew. Chem., Int. Ed. Engl. 1994, 33, 687.
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33749666016
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( 6) For intramolecular hetero-Michael additions used in the synthesis of tetrahydropyrans, see: (a) Maurer, B.; Grieder, A.; Thommen, W. Helv. Chim. Acta 1979, 62, 44. (b) Seebach, D.; Pohmakotr, M. Helv. Chim. Acta 1979, 62, 843. (c) Kozikowski, A. P.; Schmiesing, R. J.; Sorgi, K. L. J. Am. Chem. Soc. 1980, 102, 6577. (d) Bates, H. A.; Deng, P.-N. J. Org. Chem. 1983, 48, 4479. (e) Crimmins, M. T.; O'Mahony, R. J. Org. Chem. 1989, 54, 1157. (f) Allevi, P.; Ciuffreda, P.; Colombo, D.; Monti, D.; Speranza, G.; Manitto, P. J. Chem. Soc., Perkin Trans. 1, 1989, 1281. (g) Kim, S.; Salomon, R. G. Tetrahedron Lett. 1989, 30, 6279. (h) Nicolaou, K. C.; Hwang, C.-K.; Duggan, M. E. J. Am. Chem. Soc. 1989, 111, 6682. (i). Hori, K.; Hikage, N.; Inagaki, A.; Mori, S.; Nomura, K.; Yoshii, E. J. Org. Chem. 1992, 57, 2888. (j) Aicher, T. D.; Buszek, K. R.; Fang, F. G.; Forsyth, C. J.; Jung, S. H.; Kishi, Y.; Scola, P. M. Tetrahedron Lett. 1992, 33, 1549. (k) Machinaga, N.; Kibayashi, C. Tetrahedron Lett. 1993, 34, 5739. (1) Dheilly, L.; Lièvre, C.; Fréehou, C.; Demailly, G. Tetrahedron Lett. 1993, 34, 5895. (m) Horita, K.; Hachiya, S.; Nagasawa, M., Hikota, M.; Yonemitsu, O. Synlett 1994, 38. (n) Roedern, E. G.; Kessler, H. Angew. Chem., Int. Ed. Engl. 1994, 33, 687.
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85033135619
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note
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Semiempirical calculations using MOPAC/AM1 for the four possible enolates obtained in the cyclization, without countercation, in accordance with the criterion outlined in Figure 1 showed the following heats of formation: ec-ax (-160.88 kcal/mol), ax-ec (-160.95 kcal/mol), ec-ec (-161.14 kcal/mol), and ax-ax (-164.47 kcal/mol).
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49
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1542585811
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Since sodium parametrization is not available, a "sparkles" entity was used, considering its definition as a simplified atom of nuclear charge of + 1, ionic radius of 0.7 Å, and zero heat of formation, no orbitals and no ionization potential. Stewart, J. J. P. MOPAC Manual, 1990.
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0001651476
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The Z conformation is also the preferred one for the free enolates obtained from saturated esters: (a) Wang, X.; Houk, K. N. J. Am. Chem. Soc. 1988, 110, 1870. (b) Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872.
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33845278614
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The Z conformation is also the preferred one for the free enolates obtained from saturated esters: (a) Wang, X.; Houk, K. N. J. Am. Chem. Soc. 1988, 110, 1870. (b) Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872.
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85033136594
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Calibration of the obtained results was performed using the higher basis set level 6-31+G*. Reference 24
-
Calibration of the obtained results was performed using the higher basis set level 6-31+G*. Reference 24.
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0001273451
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3-21G//3-21G total energy of structures of Figure 6 in hartree: (a) -1149.707 41. (b) -1149.755 68. (c) -1149.737 05
-
3-21G//3-21G total energy of structures of Figure 6 in hartree: (a) -1149.707 41. (b) -1149.755 68. (c) -1149.737 05.
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