A DFT computational study on electrophilic substitutions upon α-oxy-substituted benzylorganolithium compounds: Lithium catalysis is the hidden piece of the puzzle

Journal of the American Chemical Society

Volumn 126, Issue 51, 2004, Pages 16738-16739

  Capó, Magdalena ^a   Saá, José M ^a  

^a UNIVERSITAT DE LES ILLES BALEARS   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

BENZYLORGANOLITHIUM; LITHIUM DERIVATIVE; UNCLASSIFIED DRUG;

ACYLATION; ALKYLATION; ARTICLE; CATALYSIS; DENSITY FUNCTIONAL THEORY; RACEMIZATION; REACTION ANALYSIS; SOLVATION; STEREOCHEMISTRY; SUBSTITUTION REACTION; X RAY ANALYSIS;

EID: 11244306545     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja045203s     Document Type: Article

References (45)

1. Basil, A.; Thayumanavan, S. Angew. Chem., Int. Ed. 2002, 41, 717. Clayden, J. Organolithium Selectivity for Synthesis; Pergamon Press: Oxford, UK, 2002. Topics in Organometallic Chemistry, Hodgson, D. M., Ed.; Springer-Verlag: Berlin, 2003; Vol. 5.
2. Basil, A.; Thayumanavan, S. Angew. Chem., Int. Ed. 2002, 41, 717. Clayden, J. Organolithium Selectivity for Synthesis; Pergamon Press: Oxford, UK, 2002. Topics in Organometallic Chemistry, Hodgson, D. M., Ed.; Springer-Verlag: Berlin, 2003; Vol. 5.
3. Basil, A.; Thayumanavan, S. Angew. Chem., Int. Ed. 2002, 41, 717. Clayden, J. Organolithium Selectivity for Synthesis; Pergamon Press: Oxford, UK, 2002. Topics in Organometallic Chemistry, Hodgson, D. M., Ed.; Springer-Verlag: Berlin, 2003; Vol. 5.
4. Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097.
5. Hammerschmidt, F.; Hanninger, A. Chem. Ber. 1995, 128, 1069.
6. Derwing, C.; Frank, H.; Hoppe, D. Eur. J. Org. Chem. 1999, 3519.
7. Faibish, N. C.; Park, J. S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1997, 119, 11561.
8. Wu, S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1996, 118, 715.
9. Basu, A.; Beak, P. J. Am. Chem. Soc. 1996, 118, 1575.
10. Nakamura, S.; Nakagawa, R.; Watanabe Y.; Toru, T. J. Am. Chem. Soc. 2000, 122, 11340.
11. (a) Polarity: Schlosser, M.; Limat, D. J. Am. Chem. Soc. 1995, 117, 12342. Hoppe, I.; Marsh, M.; Harms, K.; Boche, G.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 2185. Rein, K.; Goicoechea-Pappas, M.; Anklekar, T. V.; Hart, G. C.; Smith, G. A.; Gawley, R. E. J. Am. Chem. Soc. 1989, 111, 2211.
12. (a) Polarity: Schlosser, M.; Limat, D. J. Am. Chem. Soc. 1995, 117, 12342. Hoppe, I.; Marsh, M.; Harms, K.; Boche, G.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 2185. Rein, K.; Goicoechea-Pappas, M.; Anklekar, T. V.; Hart, G. C.; Smith, G. A.; Gawley, R. E. J. Am. Chem. Soc. 1989, 111, 2211.
13. (a) Polarity: Schlosser, M.; Limat, D. J. Am. Chem. Soc. 1995, 117, 12342. Hoppe, I.; Marsh, M.; Harms, K.; Boche, G.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 2185. Rein, K.; Goicoechea-Pappas, M.; Anklekar, T. V.; Hart, G. C.; Smith, G. A.; Gawley, R. E. J. Am. Chem. Soc. 1989, 111, 2211.
14. (b) Leaving group: Thayumanavan, S.; Lee, S.; Liao, C.; Beak, P. J. Am. Chem. Soc. 1994, 116, 9755. Behrens, K.; Frölich, R.; Meyer, O.; Hoppe, D. Eur. J. Org. Chem. 1998, 2397.
15. (b) Leaving group: Thayumanavan, S.; Lee, S.; Liao, C.; Beak, P. J. Am. Chem. Soc. 1994, 116, 9755. Behrens, K.; Frölich, R.; Meyer, O.; Hoppe, D. Eur. J. Org. Chem. 1998, 2397.
16. (c) Temperature: Curtis, M. D.; Beak, P. J. Org. Chem. 1999, 64, 16. Pipple, D. J.; Weisenburger, G. A.; Wilson, S. R.; Beak, P. Angew. Chem., Int. Ed. 1998, 37, 2522. Park, Y. S.; Weisenburger, G. A.; Beak, P. J. Am. Chem. Soc. 1997, 119, 10537. Weisenburger, G. A.; Beak, P. J. Am. Chem. Soc. 1996, 118, 12218.
17. (c) Temperature: Curtis, M. D.; Beak, P. J. Org. Chem. 1999, 64, 16. Pipple, D. J.; Weisenburger, G. A.; Wilson, S. R.; Beak, P. Angew. Chem., Int. Ed. 1998, 37, 2522. Park, Y. S.; Weisenburger, G. A.; Beak, P. J. Am. Chem. Soc. 1997, 119, 10537. Weisenburger, G. A.; Beak, P. J. Am. Chem. Soc. 1996, 118, 12218.
18. (c) Temperature: Curtis, M. D.; Beak, P. J. Org. Chem. 1999, 64, 16. Pipple, D. J.; Weisenburger, G. A.; Wilson, S. R.; Beak, P. Angew. Chem., Int. Ed. 1998, 37, 2522. Park, Y. S.; Weisenburger, G. A.; Beak, P. J. Am. Chem. Soc. 1997, 119, 10537. Weisenburger, G. A.; Beak, P. J. Am. Chem. Soc. 1996, 118, 12218.
19. (c) Temperature: Curtis, M. D.; Beak, P. J. Org. Chem. 1999, 64, 16. Pipple, D. J.; Weisenburger, G. A.; Wilson, S. R.; Beak, P. Angew. Chem., Int. Ed. 1998, 37, 2522. Park, Y. S.; Weisenburger, G. A.; Beak, P. J. Am. Chem. Soc. 1997, 119, 10537. Weisenburger, G. A.; Beak, P. J. Am. Chem. Soc. 1996, 118, 12218.
20. (d) Other: Meyers, A. I.; Warmus, J. S.; Gonzalez, M. A.; Guiles, J.; Akahane, A. Tetrahedron Lett. 1991, 32, 5509.
21. (a) Matulenko, M.; Meyers, A. I. J. Org. Chem. 1996, 61, 573.
22. (b) Gawley, R. E.; Low, E.; Zhang, Q.; Harris, R. J. Am. Chem. Soc. 2000, 122, 3344.
23. Weisenburger, G. A.; Faibish, N. C.; Pippel, D. J.; Beak, P. J. Am. Chem. Soc. 1999, 121, 9522.
24. To be published in due course.
25. Ruhland, T.; Dress, R.; Hoffmann, R. W. Angew. Chem., Int. Ed. Engl. 1993, 32, 1467. Reich, H. L.; Dykstra, R. R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1469.
26. Ruhland, T.; Dress, R.; Hoffmann, R. W. Angew. Chem., Int. Ed. Engl. 1993, 32, 1467. Reich, H. L.; Dykstra, R. R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1469.
27. For electrophilic catalysis by ionic salts see: Westaway, K. C.; Gao, Y.; Fang, Y. J. Org. Chem. 2003, 68, 3084. Smith, P. J.; Crowe, D. A.; Westaway, K. C. Can. J. Chem. 2001, 79, 1145. Zavada, J.; Pankova, M.; Vitek, A. Collect. Czech. Chem. Commun. 1981, 46, 3247.
28. For electrophilic catalysis by ionic salts see: Westaway, K. C.; Gao, Y.; Fang, Y. J. Org. Chem. 2003, 68, 3084. Smith, P. J.; Crowe, D. A.; Westaway, K. C. Can. J. Chem. 2001, 79, 1145. Zavada, J.; Pankova, M.; Vitek, A. Collect. Czech. Chem. Commun. 1981, 46, 3247.
29. For electrophilic catalysis by ionic salts see: Westaway, K. C.; Gao, Y.; Fang, Y. J. Org. Chem. 2003, 68, 3084. Smith, P. J.; Crowe, D. A.; Westaway, K. C. Can. J. Chem. 2001, 79, 1145. Zavada, J.; Pankova, M.; Vitek, A. Collect. Czech. Chem. Commun. 1981, 46, 3247.
30. N2 displacements See: Harder, S.; Streitwieser, A., Jr.; Petty, J. T.; Schleyer, P. v. R. J. Am. Chem. Soc. 1995, 117, 3253. Harder, S.; van Lenthe, J. H.; van Eikema Hommes, N. J. R.; Schleyer, P.v. R. J. Am. Chem. Soc. 1994, 116, 2508. Mori, S.; Nakamura, E.; Morokuma, K. J. Am. Chem. Soc. 2000, 122, 7294.
31. N2 displacements See: Harder, S.; Streitwieser, A., Jr.; Petty, J. T.; Schleyer, P. v. R. J. Am. Chem. Soc. 1995, 117, 3253. Harder, S.; van Lenthe, J. H.; van Eikema Hommes, N. J. R.; Schleyer, P.v. R. J. Am. Chem. Soc. 1994, 116, 2508. Mori, S.; Nakamura, E.; Morokuma, K. J. Am. Chem. Soc. 2000, 122, 7294.
32. N2 displacements See: Harder, S.; Streitwieser, A., Jr.; Petty, J. T.; Schleyer, P. v. R. J. Am. Chem. Soc. 1995, 117, 3253. Harder, S.; van Lenthe, J. H.; van Eikema Hommes, N. J. R.; Schleyer, P.v. R. J. Am. Chem. Soc. 1994, 116, 2508. Mori, S.; Nakamura, E.; Morokuma, K. J. Am. Chem. Soc. 2000, 122, 7294.
33. Reich, H. J.; Sanders, A. W.; Fiedler, A. T.; Bevan, M. J. J. Am. Chem. Soc. 2002, 124, 13386.
34. Zarges, W.; Marsch, M.; Harms, K.; Boche, G. Chem. Ber. 1989, 122, 2299. Marsch, M.; Harms, K.; Zschage, O.; Hoppe, D.; Boche, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 321. Boche, G.; Marsch, M.; Harbach, J.; Harms, K.; Ledig, B.; Schubert, F.; Lorentz, J. C. W.; Ahlbrecht, H. Chem. Ber. 1993, 126, 1887. Zarges, W.; Marsch, M.; Harms, K.; Koch, W.; Frenking, G.; Boche, G. Chem. Ber. 1991, 124, 543.
35. Zarges, W.; Marsch, M.; Harms, K.; Boche, G. Chem. Ber. 1989, 122, 2299. Marsch, M.; Harms, K.; Zschage, O.; Hoppe, D.; Boche, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 321. Boche, G.; Marsch, M.; Harbach, J.; Harms, K.; Ledig, B.; Schubert, F.; Lorentz, J. C. W.; Ahlbrecht, H. Chem. Ber. 1993, 126, 1887. Zarges, W.; Marsch, M.; Harms, K.; Koch, W.; Frenking, G.; Boche, G. Chem. Ber. 1991, 124, 543.
36. Zarges, W.; Marsch, M.; Harms, K.; Boche, G. Chem. Ber. 1989, 122, 2299. Marsch, M.; Harms, K.; Zschage, O.; Hoppe, D.; Boche, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 321. Boche, G.; Marsch, M.; Harbach, J.; Harms, K.; Ledig, B.; Schubert, F.; Lorentz, J. C. W.; Ahlbrecht, H. Chem. Ber. 1993, 126, 1887. Zarges, W.; Marsch, M.; Harms, K.; Koch, W.; Frenking, G.; Boche, G. Chem. Ber. 1991, 124, 543.
37. Zarges, W.; Marsch, M.; Harms, K.; Boche, G. Chem. Ber. 1989, 122, 2299. Marsch, M.; Harms, K.; Zschage, O.; Hoppe, D.; Boche, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 321. Boche, G.; Marsch, M.; Harbach, J.; Harms, K.; Ledig, B.; Schubert, F.; Lorentz, J. C. W.; Ahlbrecht, H. Chem. Ber. 1993, 126, 1887. Zarges, W.; Marsch, M.; Harms, K.; Koch, W.; Frenking, G.; Boche, G. Chem. Ber. 1991, 124, 543.
38. Saá, J. M. Helv. Chim. Acta 2002, 85, 814 and references therein.
39. Beno, M. A.; Hope, H.; Olmstead, M. M.; Power, P. P. Organometallics 1985, 4, 2117. Brooks, J. J.; Stucky, G. D. J. Am. Chem. Soc. 1972, 94, 7333. Engelhardt, L. M.; Leung, W.-P.; Raston, C. L.; Twiss, P.; White, A. H. J. Chem. Soc., Dalton Trans, 1984, 321.
40. Beno, M. A.; Hope, H.; Olmstead, M. M.; Power, P. P. Organometallics 1985, 4, 2117. Brooks, J. J.; Stucky, G. D. J. Am. Chem. Soc. 1972, 94, 7333. Engelhardt, L. M.; Leung, W.-P.; Raston, C. L.; Twiss, P.; White, A. H. J. Chem. Soc., Dalton Trans, 1984, 321.
41. Beno, M. A.; Hope, H.; Olmstead, M. M.; Power, P. P. Organometallics 1985, 4, 2117. Brooks, J. J.; Stucky, G. D. J. Am. Chem. Soc. 1972, 94, 7333. Engelhardt, L. M.; Leung, W.-P.; Raston, C. L.; Twiss, P.; White, A. H. J. Chem. Soc., Dalton Trans, 1984, 321.
42. 2), i.e., higher than those found for 1cip-2e (see the text).
43. Ma, J. C.; Dougherty, D. A. Chem. Rev. 1997, 97, 1303.
44. -1 higher in energy than that involving contact ion pair species 1cip-2e. Bulk solvation as defined by Tomasi's PCM model did not modify significantly this analysis (data not shown). See Cossi, M.; Barone, V.; Mennucci, B.; Tomasi, J. Chem. Phys. Lett. 1998, 286, 253 and references therein.
45. -1, respectively. JA045203S