The SN2 reaction in the solid state. An unusual, BAl2 aminolysis of an ester group in crystalline (±)-2-amino-2′-hydroxy-3′-(methoxycarbonyl)-1,1′- binaphthyl elucidated by X-ray diffraction and isotopic labeling. New experimental evidence for linearity in SN2 substitution

Journal of the American Chemical Society

Volumn 118, Issue 2, 1996, Pages 487-488

  Smrčina, Martin ^a   Vyskočil, Štěpán ^a   Hanüš, Vladimír ^b   Polášek, Miroslav ^b   Langer, Vratislav ^c   Chew, Benjamin G M ^d   Zax, David B ^d   Verrier, Hugh ^e   Harper, Kevin ^f   Claxton, Thomas A ^g   Kočovský, Pavel ^g  

^a CHARLES UNIVERSITY   (Czech Republic)

^b J HEYROVSKÝ INSTITUTE OF PHYSICAL CHEMISTRY   (Czech Republic)

^c CHALMERS UNIVERSITY OF TECHNOLOGY   (Sweden)

^d Department of Molecular Biology and Genetics   (United States)

^e NEUROSCIENCE RESEARCH CENTRE   (United Kingdom)

^f Hickson Fine Chemicals   (United Kingdom)

^g UNIVERSITY OF LEICESTER   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

1,1' BINAPHTHYL DERIVATIVE;

ARTICLE; DRUG STRUCTURE; NUCLEAR MAGNETIC RESONANCE; X RAY DIFFRACTION;

EID: 0030026966     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja951920y     Document Type: Article

References (52)

1. For reviews on binaphthyls, see: (a) Rosini, C.; Franzini, L.; Raffaelli, A.; Salvadori, P. Synthesis 1992, 503. (b) Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley & Sons: New York, 1994.
2. For reviews on binaphthyls, see: (a) Rosini, C.; Franzini, L.; Raffaelli, A.; Salvadori, P. Synthesis 1992, 503. (b) Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley & Sons: New York, 1994.
3. For examples of this chiral amplification, see ref 1b and the following: (a) Terada, M.; Mikami, K.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623. (b) Mikami, K.; Motoyama, Y.; Terada, M. J. Am. Chem. Soc. 1994, 116, 2812. (c) Terada, M.; Mikami, K. J. Chem. Soc., Chem. Commun. 1994, 833. (d) Kobayashi, S.; Ishitani, H.; Araki, M.; Hachiya, I. Tetrahedron Lett. 1994, 35, 6325. (e) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. J. Am. Chem. Soc. 1994, 116, 9430. (f) Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; J. Wiley: New York, 1994.
4. For examples of this chiral amplification, see ref 1b and the following: (a) Terada, M.; Mikami, K.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623. (b) Mikami, K.; Motoyama, Y.; Terada, M. J. Am. Chem. Soc. 1994, 116, 2812. (c) Terada, M.; Mikami, K. J. Chem. Soc., Chem. Commun. 1994, 833. (d) Kobayashi, S.; Ishitani, H.; Araki, M.; Hachiya, I. Tetrahedron Lett. 1994, 35, 6325. (e) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. J. Am. Chem. Soc. 1994, 116, 9430. (f) Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; J. Wiley: New York, 1994.
5. For examples of this chiral amplification, see ref 1b and the following: (a) Terada, M.; Mikami, K.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623. (b) Mikami, K.; Motoyama, Y.; Terada, M. J. Am. Chem. Soc. 1994, 116, 2812. (c) Terada, M.; Mikami, K. J. Chem. Soc., Chem. Commun. 1994, 833. (d) Kobayashi, S.; Ishitani, H.; Araki, M.; Hachiya, I. Tetrahedron Lett. 1994, 35, 6325. (e) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. J. Am. Chem. Soc. 1994, 116, 9430. (f) Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; J. Wiley: New York, 1994.
6. For examples of this chiral amplification, see ref 1b and the following: (a) Terada, M.; Mikami, K.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623. (b) Mikami, K.; Motoyama, Y.; Terada, M. J. Am. Chem. Soc. 1994, 116, 2812. (c) Terada, M.; Mikami, K. J. Chem. Soc., Chem. Commun. 1994, 833. (d) Kobayashi, S.; Ishitani, H.; Araki, M.; Hachiya, I. Tetrahedron Lett. 1994, 35, 6325. (e) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. J. Am. Chem. Soc. 1994, 116, 9430. (f) Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; J. Wiley: New York, 1994.
7. For examples of this chiral amplification, see ref 1b and the following: (a) Terada, M.; Mikami, K.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623. (b) Mikami, K.; Motoyama, Y.; Terada, M. J. Am. Chem. Soc. 1994, 116, 2812. (c) Terada, M.; Mikami, K. J. Chem. Soc., Chem. Commun. 1994, 833. (d) Kobayashi, S.; Ishitani, H.; Araki, M.; Hachiya, I. Tetrahedron Lett. 1994, 35, 6325. (e) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. J. Am. Chem. Soc. 1994, 116, 9430. (f) Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; J. Wiley: New York, 1994.
8. For examples of this chiral amplification, see ref 1b and the following: (a) Terada, M.; Mikami, K.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623. (b) Mikami, K.; Motoyama, Y.; Terada, M. J. Am. Chem. Soc. 1994, 116, 2812. (c) Terada, M.; Mikami, K. J. Chem. Soc., Chem. Commun. 1994, 833. (d) Kobayashi, S.; Ishitani, H.; Araki, M.; Hachiya, I. Tetrahedron Lett. 1994, 35, 6325. (e) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. J. Am. Chem. Soc. 1994, 116, 9430. (f) Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; J. Wiley: New York, 1994.
9. For reviews on solid-state organic reactions, see: (a) Green, B. S.; Aradyellin, R.; Cohen, M. D. Top. Stereochem. 1986, 16, 131. (b) Toda, F. Synlett 1993, 303. Singh, N. B.; Singh, R. J.; Singh, N. P. Tetrahedron 1994, 50, 6441.
10. For reviews on solid-state organic reactions, see: (a) Green, B. S.; Aradyellin, R.; Cohen, M. D. Top. Stereochem. 1986, 16, 131. (b) Toda, F. Synlett 1993, 303. Singh, N. B.; Singh, R. J.; Singh, N. P. Tetrahedron 1994, 50, 6441.
11. For reviews on solid-state organic reactions, see: (a) Green, B. S.; Aradyellin, R.; Cohen, M. D. Top. Stereochem. 1986, 16, 131. (b) Toda, F. Synlett 1993, 303. Singh, N. B.; Singh, R. J.; Singh, N. P. Tetrahedron 1994, 50, 6441.
12. N2 reactions in the solid state by X-ray analysis see: (a) Sukenik, C. N.; Bonapace, J. A. P.; Mandel, N. S.; Lau, P.-Y.; Wood, G.; Bergman, R. G. J. Am. Chem. Soc. 1977, 99, 851. (b) Sarma, J.; Dunitz, J. D. Acta Crystallogr. 1990, 46, 780. (c) Venugopalan, P.; Venkatesan, K.; Klausen, J.; Novotny-Bregger, E.; Leumann, C.; Eschenmoser, A.; Dunitz, J. D. Helv. Chim. Acta 1991, 74, 662. (d) Dessolin, M.; Eisenstein, O.; Golfier, M.; Prangé, T.; Sautet, P. J. Chem. Soc., Chem. Commun. 1992, 132.
13. N2 reactions in the solid state by X-ray analysis see: (a) Sukenik, C. N.; Bonapace, J. A. P.; Mandel, N. S.; Lau, P.-Y.; Wood, G.; Bergman, R. G. J. Am. Chem. Soc. 1977, 99, 851. (b) Sarma, J.; Dunitz, J. D. Acta Crystallogr. 1990, 46, 780. (c) Venugopalan, P.; Venkatesan, K.; Klausen, J.; Novotny-Bregger, E.; Leumann, C.; Eschenmoser, A.; Dunitz, J. D. Helv. Chim. Acta 1991, 74, 662. (d) Dessolin, M.; Eisenstein, O.; Golfier, M.; Prangé, T.; Sautet, P. J. Chem. Soc., Chem. Commun. 1992, 132.
14. N2 reactions in the solid state by X-ray analysis see: (a) Sukenik, C. N.; Bonapace, J. A. P.; Mandel, N. S.; Lau, P.-Y.; Wood, G.; Bergman, R. G. J. Am. Chem. Soc. 1977, 99, 851. (b) Sarma, J.; Dunitz, J. D. Acta Crystallogr. 1990, 46, 780. (c) Venugopalan, P.; Venkatesan, K.; Klausen, J.; Novotny-Bregger, E.; Leumann, C.; Eschenmoser, A.; Dunitz, J. D. Helv. Chim. Acta 1991, 74, 662. (d) Dessolin, M.; Eisenstein, O.; Golfier, M.; Prangé, T.; Sautet, P. J. Chem. Soc., Chem. Commun. 1992, 132.
15. N2 reactions in the solid state by X-ray analysis see: (a) Sukenik, C. N.; Bonapace, J. A. P.; Mandel, N. S.; Lau, P.-Y.; Wood, G.; Bergman, R. G. J. Am. Chem. Soc. 1977, 99, 851. (b) Sarma, J.; Dunitz, J. D. Acta Crystallogr. 1990, 46, 780. (c) Venugopalan, P.; Venkatesan, K.; Klausen, J.; Novotny-Bregger, E.; Leumann, C.; Eschenmoser, A.; Dunitz, J. D. Helv. Chim. Acta 1991, 74, 662. (d) Dessolin, M.; Eisenstein, O.; Golfier, M.; Prangé, T.; Sautet, P. J. Chem. Soc., Chem. Commun. 1992, 132.
16. Smrčina, M.; Vyskočil, Š.; Máca, B.; Polášek, M.; Claxton, T.; Abbott, A. P.; Kočovský, P. J. Org. Chem. 1994, 59, 2156.
17. For related examples, see: (a) Yamamoto, K.; Yumioka, H.; Okamoto, Y.; Chikamatsu, H. J. Chem. Soc., Chem. Commun. 1987, 168. (b) Hovorka, M.; Ščigel, R.; Günterová, J.; Tichý, M.; Závada, J. Tetrahedron 1992, 48, 9503. (c) Smrčina, M.; Lorenc, M.; Hanuš, V.; Sedmera, P.; Kočovský, P. J. Org. Chem. 1992, 57, 1917. (d) Smrčina, M.; Poláková, J.; Vyskočil, S.; Kočovský, P. J. Org. Chem. 1993, 58, 4534. (e) Jung, M. E.; Kim, C.; von dem Bussche, L. J. Org. Chem. 1994, 59, 3248.
18. For related examples, see: (a) Yamamoto, K.; Yumioka, H.; Okamoto, Y.; Chikamatsu, H. J. Chem. Soc., Chem. Commun. 1987, 168. (b) Hovorka, M.; Ščigel, R.; Günterová, J.; Tichý, M.; Závada, J. Tetrahedron 1992, 48, 9503. (c) Smrčina, M.; Lorenc, M.; Hanuš, V.; Sedmera, P.; Kočovský, P. J. Org. Chem. 1992, 57, 1917. (d) Smrčina, M.; Poláková, J.; Vyskočil, S.; Kočovský, P. J. Org. Chem. 1993, 58, 4534. (e) Jung, M. E.; Kim, C.; von dem Bussche, L. J. Org. Chem. 1994, 59, 3248.
19. For related examples, see: (a) Yamamoto, K.; Yumioka, H.; Okamoto, Y.; Chikamatsu, H. J. Chem. Soc., Chem. Commun. 1987, 168. (b) Hovorka, M.; Ščigel, R.; Günterová, J.; Tichý, M.; Závada, J. Tetrahedron 1992, 48, 9503. (c) Smrčina, M.; Lorenc, M.; Hanuš, V.; Sedmera, P.; Kočovský, P. J. Org. Chem. 1992, 57, 1917. (d) Smrčina, M.; Poláková, J.; Vyskočil, S.; Kočovský, P. J. Org. Chem. 1993, 58, 4534. (e) Jung, M. E.; Kim, C.; von dem Bussche, L. J. Org. Chem. 1994, 59, 3248.
20. For related examples, see: (a) Yamamoto, K.; Yumioka, H.; Okamoto, Y.; Chikamatsu, H. J. Chem. Soc., Chem. Commun. 1987, 168. (b) Hovorka, M.; Ščigel, R.; Günterová, J.; Tichý, M.; Závada, J. Tetrahedron 1992, 48, 9503. (c) Smrčina, M.; Lorenc, M.; Hanuš, V.; Sedmera, P.; Kočovský, P. J. Org. Chem. 1992, 57, 1917. (d) Smrčina, M.; Poláková, J.; Vyskočil, S.; Kočovský, P. J. Org. Chem. 1993, 58, 4534. (e) Jung, M. E.; Kim, C.; von dem Bussche, L. J. Org. Chem. 1994, 59, 3248.
21. For related examples, see: (a) Yamamoto, K.; Yumioka, H.; Okamoto, Y.; Chikamatsu, H. J. Chem. Soc., Chem. Commun. 1987, 168. (b) Hovorka, M.; Ščigel, R.; Günterová, J.; Tichý, M.; Závada, J. Tetrahedron 1992, 48, 9503. (c) Smrčina, M.; Lorenc, M.; Hanuš, V.; Sedmera, P.; Kočovský, P. J. Org. Chem. 1992, 57, 1917. (d) Smrčina, M.; Poláková, J.; Vyskočil, S.; Kočovský, P. J. Org. Chem. 1993, 58, 4534. (e) Jung, M. E.; Kim, C.; von dem Bussche, L. J. Org. Chem. 1994, 59, 3248.
22. .+.
23. This sample exhibited changes in the spectrum during the scanning (at 150 °C) so that the spectrum at the beginning of evaporation was not entirely identical to that obtained toward the end. This suggests a chemical reaction proceeding in the direct inlet. By contrast, the FAB spectrum was fully compatible with the structure 3. The presence of the low-intensity satellite ions m/z 357 (M + 14) and 329 (M - 14) in the EIMS can be attributed to the contamination by homologues.
24. Refluxing for 24 h led to a partial decomposition rather than to the formation of 4.
25. A slow 3 → 4 conversion occurs in the crystal at room temperature as revealed by the analysis of aged samples. For a similar observation, see ref 4c.
26. 3 solution (30.5 ppm).
27. -1), was observed at 230-245 °C.
28. Al2 mechanism (in solution), see: (a) Ingold, K. C. Structure and Mechanism in Organic Chemistry: Cornell University Press: Ithaca, NY, 1953: p 765. (b) March, J. Advanced Organic Chemistry, 4th ed.: J. Wiley & Sons: New York, 1992: p 380. (c) Druganov, A. G.; Ankrushina, N. A. Khim. Prir. Soedin. 1990, 693. (d) Cacciapaglia, R.; Mandolini, L.; Castelli, V. V. Recl. Trav. Chim. Pays-Bas 1993, 112, 347. (e) Douglas, J. E.; Campbell, G.; Wigfield, D. C. Can. J. Chem. 1993, 71, 1841.
29. Al2 mechanism (in solution), see: (a) Ingold, K. C. Structure and Mechanism in Organic Chemistry: Cornell University Press: Ithaca, NY, 1953: p 765. (b) March, J. Advanced Organic Chemistry, 4th ed.: J. Wiley & Sons: New York, 1992: p 380. (c) Druganov, A. G.; Ankrushina, N. A. Khim. Prir. Soedin. 1990, 693. (d) Cacciapaglia, R.; Mandolini, L.; Castelli, V. V. Recl. Trav. Chim. Pays-Bas 1993, 112, 347. (e) Douglas, J. E.; Campbell, G.; Wigfield, D. C. Can. J. Chem. 1993, 71, 1841.
30. Al2 mechanism (in solution), see: (a) Ingold, K. C. Structure and Mechanism in Organic Chemistry: Cornell University Press: Ithaca, NY, 1953: p 765. (b) March, J. Advanced Organic Chemistry, 4th ed.: J. Wiley & Sons: New York, 1992: p 380. (c) Druganov, A. G.; Ankrushina, N. A. Khim. Prir. Soedin. 1990, 693. (d) Cacciapaglia, R.; Mandolini, L.; Castelli, V. V. Recl. Trav. Chim. Pays-Bas 1993, 112, 347. (e) Douglas, J. E.; Campbell, G.; Wigfield, D. C. Can. J. Chem. 1993, 71, 1841.
31. Al2 mechanism (in solution), see: (a) Ingold, K. C. Structure and Mechanism in Organic Chemistry: Cornell University Press: Ithaca, NY, 1953: p 765. (b) March, J. Advanced Organic Chemistry, 4th ed.: J. Wiley & Sons: New York, 1992: p 380. (c) Druganov, A. G.; Ankrushina, N. A. Khim. Prir. Soedin. 1990, 693. (d) Cacciapaglia, R.; Mandolini, L.; Castelli, V. V. Recl. Trav. Chim. Pays-Bas 1993, 112, 347. (e) Douglas, J. E.; Campbell, G.; Wigfield, D. C. Can. J. Chem. 1993, 71, 1841.
32. Al2 mechanism (in solution), see: (a) Ingold, K. C. Structure and Mechanism in Organic Chemistry: Cornell University Press: Ithaca, NY, 1953: p 765. (b) March, J. Advanced Organic Chemistry, 4th ed.: J. Wiley & Sons: New York, 1992: p 380. (c) Druganov, A. G.; Ankrushina, N. A. Khim. Prir. Soedin. 1990, 693. (d) Cacciapaglia, R.; Mandolini, L.; Castelli, V. V. Recl. Trav. Chim. Pays-Bas 1993, 112, 347. (e) Douglas, J. E.; Campbell, G.; Wigfield, D. C. Can. J. Chem. 1993, 71, 1841.
33. N2, see: (a) Tenud, L.; Farooq, S.; Seibl, J.; Eschenmoser, A. Helv. Chim. Acta 1970, 53, 2059. (b) Baldwin, J. E. J. Chem. Commun. 1976, 734. (c) King, J. F.; McGarrity, M. J. J. Chem. Soc., Chem. Commun. 1979, 1140. (d) Menger, M. Tetrahedron 1983, 39, 1013. X-ray evidence: ref 4 and the following: (e) Britton, D.; Dunitz, J. D. Helv. Chim. Acta 1980, 63, 1068. Quantum chemistry approach: (f) Wang, H.; Peslherbe, G. H.; Hase, W. L. J. Am. Chem. Soc. 1994, 116, 9644 and references cited therein.
34. N2, see: (a) Tenud, L.; Farooq, S.; Seibl, J.; Eschenmoser, A. Helv. Chim. Acta 1970, 53, 2059. (b) Baldwin, J. E. J. Chem. Commun. 1976, 734. (c) King, J. F.; McGarrity, M. J. J. Chem. Soc., Chem. Commun. 1979, 1140. (d) Menger, M. Tetrahedron 1983, 39, 1013. X-ray evidence: ref 4 and the following: (e) Britton, D.; Dunitz, J. D. Helv. Chim. Acta 1980, 63, 1068. Quantum chemistry approach: (f) Wang, H.; Peslherbe, G. H.; Hase, W. L. J. Am. Chem. Soc. 1994, 116, 9644 and references cited therein.
35. N2, see: (a) Tenud, L.; Farooq, S.; Seibl, J.; Eschenmoser, A. Helv. Chim. Acta 1970, 53, 2059. (b) Baldwin, J. E. J. Chem. Commun. 1976, 734. (c) King, J. F.; McGarrity, M. J. J. Chem. Soc., Chem. Commun. 1979, 1140. (d) Menger, M. Tetrahedron 1983, 39, 1013. X-ray evidence: ref 4 and the following: (e) Britton, D.; Dunitz, J. D. Helv. Chim. Acta 1980, 63, 1068. Quantum chemistry approach: (f) Wang, H.; Peslherbe, G. H.; Hase, W. L. J. Am. Chem. Soc. 1994, 116, 9644 and references cited therein.
36. N2, see: (a) Tenud, L.; Farooq, S.; Seibl, J.; Eschenmoser, A. Helv. Chim. Acta 1970, 53, 2059. (b) Baldwin, J. E. J. Chem. Commun. 1976, 734. (c) King, J. F.; McGarrity, M. J. J. Chem. Soc., Chem. Commun. 1979, 1140. (d) Menger, M. Tetrahedron 1983, 39, 1013. X-ray evidence: ref 4 and the following: (e) Britton, D.; Dunitz, J. D. Helv. Chim. Acta 1980, 63, 1068. Quantum chemistry approach: (f) Wang, H.; Peslherbe, G. H.; Hase, W. L. J. Am. Chem. Soc. 1994, 116, 9644 and references cited therein.
37. N2, see: (a) Tenud, L.; Farooq, S.; Seibl, J.; Eschenmoser, A. Helv. Chim. Acta 1970, 53, 2059. (b) Baldwin, J. E. J. Chem. Commun. 1976, 734. (c) King, J. F.; McGarrity, M. J. J. Chem. Soc., Chem. Commun. 1979, 1140. (d) Menger, M. Tetrahedron 1983, 39, 1013. X-ray evidence: ref 4 and the following: (e) Britton, D.; Dunitz, J. D. Helv. Chim. Acta 1980, 63, 1068. Quantum chemistry approach: (f) Wang, H.; Peslherbe, G. H.; Hase, W. L. J. Am. Chem. Soc. 1994, 116, 9644 and references cited therein.
38. N2, see: (a) Tenud, L.; Farooq, S.; Seibl, J.; Eschenmoser, A. Helv. Chim. Acta 1970, 53, 2059. (b) Baldwin, J. E. J. Chem. Commun. 1976, 734. (c) King, J. F.; McGarrity, M. J. J. Chem. Soc., Chem. Commun. 1979, 1140. (d) Menger, M. Tetrahedron 1983, 39, 1013. X-ray evidence: ref 4 and the following: (e) Britton, D.; Dunitz, J. D. Helv. Chim. Acta 1980, 63, 1068. Quantum chemistry approach: (f) Wang, H.; Peslherbe, G. H.; Hase, W. L. J. Am. Chem. Soc. 1994, 116, 9644 and references cited therein.
39. For the use of X-ray analysis in determining fundamental organic chemistry pathways, see refs 4 and 14e and the following: (a) Allen, F. H.; Kennard, O.; Taylor, R. Acc. Chem. Res. 1983, 16, 146. (b) Bürgi, H. B.; Dunitz, J. D. Acc. Chem. Res. 1983, 16, 153. (c) Beak, P. Acc. Chem. Res. 1992, 25, 215.
40. For the use of X-ray analysis in determining fundamental organic chemistry pathways, see refs 4 and 14e and the following: (a) Allen, F. H.; Kennard, O.; Taylor, R. Acc. Chem. Res. 1983, 16, 146. (b) Bürgi, H. B.; Dunitz, J. D. Acc. Chem. Res. 1983, 16, 153. (c) Beak, P. Acc. Chem. Res. 1992, 25, 215.
41. For the use of X-ray analysis in determining fundamental organic chemistry pathways, see refs 4 and 14e and the following: (a) Allen, F. H.; Kennard, O.; Taylor, R. Acc. Chem. Res. 1983, 16, 146. (b) Bürgi, H. B.; Dunitz, J. D. Acc. Chem. Res. 1983, 16, 153. (c) Beak, P. Acc. Chem. Res. 1992, 25, 215.
42. w = 0.0973 on F for observed data. The estimated error in bond lengths is 0.02 Å.
43. -1 higher in energy than the former.
44. 3 is 3.55 Å.
45. Bondi, A. J. Phys. Chem. 1964, 68, 441.
46. 4a_d) are as follows: 3.42 Å/147° and 2.9 Å/164°, respectively.
47. The reaction is presumably further boosted by the intramolecular hydrogen bonding between the phenolic OH and the C=O of the ester group.
48. 2. On a small scale, (±)-3 was resolved by chromatography on a Chiralpak AD column using a 1:1 hexane-ethanol mixture as a mobile phase. The faster moving enantiomer was identified as (R)-(+)-3 (99.2% ee); (S)-(-)-3 (98.8% ee) was slower moving.
49. 18O, according to MS.
50. 4a,d (26) The observed level of conversion (up to 95%), unusually high for a solid-state reaction, suggests a fast, zip-fastening-type process occurring along the screw-axis chain throughout an entire crystalline block. The reaction is not terminated until the collapse of the majority (93-95%) of the original crystal lattice. An alternative explanation, which would require a single crystal to single crystal transformation, can be ruled out since 4 is not isostructural with 3.
51. Al2, we refer to the elementary process of interaction between two molecules of 3.
52. Johnson, C. K. Technical Report ORNL-5138; Oak Ridge National Laboratory: Oak Ridge, TN, 1976.