Solution structure of 2-[(dimethylamino)methyl]phenyllithium

Journal of the American Chemical Society

Volumn 118, Issue 25, 1996, Pages 6074-6075

  Reich, Hans J ^a   Gudmundsson, Birgir Ö ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ORGANOLITHIUM COMPOUND;

ARTICLE; DRUG STRUCTURE; NUCLEAR MAGNETIC RESONANCE;

EID: 0030059083     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960677f     Document Type: Article

References (45)

1. (a) Reich, H. J.; Holladay, J. E. J. Am. Chem. Soc. 1995, 117, 8470.
2. (b) Reich, H. J.; Kulicke, K. J. J. Am. Chem. Soc. 1995, 117, 6621.
3. (c) Reich, H. J.; Green, D. P.; Phillips, N. H. J. Am. Chem. Soc. 1989, 111, 3444. Reich, H. J.; Green, D. P.; Phillips, N. H. J. Am. Chem. Soc. 1991, 113, 1414, footnote 16.
4. (c) Reich, H. J.; Green, D. P.; Phillips, N. H. J. Am. Chem. Soc. 1989, 111, 3444. Reich, H. J.; Green, D. P.; Phillips, N. H. J. Am. Chem. Soc. 1991, 113, 1414, footnote 16.
5. (d) Reich. H. J.; Medina, M. A.; Bowe, M. D. J. Am. Chem. Soc. 1992, 114. 11003.
6. Beak, P.: Meyers, A. I. Acc. Chem. Res. 1986, 19, 356.
7. (a) Klumpp, G. W. Recl. Trav. Chim. Pays-Bas 1986, 105, 1.
8. (b) Klumpp, G. W.; Geurink, P. J. A.; Spek, A. L.; Duisenberg, A. J. M. J. Chem. Soc., Chem. Commun. 1983, 814.
9. (c) Moene, W.; Schakel, M.; Hoogland, G. J. M.; de Kanter, F. J. J.; Klumpp, G. W.; Spek, A. L. Tetrahedron Lett. 1990, 31, 2641.
10. (d) Klumpp, G. W.; Vos M.; de Kanter, F. J. J.; Slob, C.; Krabbendam, H.; Spek, A. L. J. Am. Chem. Soc. 1985, 107, 8292.
11. (e) Vos, M.; de Kanter, F. J. J.; Schakel, M.; van Eikema Hommes, N. J. R.; Klumpp, G. W. J. Am. Chem. Soc: 1987, 109, 2187.
12. Sato, D.; Kawasaki, H.; Shimada, I.; Arata, Y.; Okamura, K.; Date, T.; Koga. K. J. Am. Chem. Soc. 1992, 114, 761.
13. Horvath, R. F.; Chan, T. H. J Org. Chem. 1989, 54, 317. Lamothe, S.; Chan, T. H. Tetrahedron Lett. 1991, 32, 1847. Hartley, R. C.; Lamothe, S.; Chan, T. H. Tetrahedron Lett. 1993, 34, 1449.
14. Horvath, R. F.; Chan, T. H. J Org. Chem. 1989, 54, 317. Lamothe, S.; Chan, T. H. Tetrahedron Lett. 1991, 32, 1847. Hartley, R. C.; Lamothe, S.; Chan, T. H. Tetrahedron Lett. 1993, 34, 1449.
15. Horvath, R. F.; Chan, T. H. J Org. Chem. 1989, 54, 317. Lamothe, S.; Chan, T. H. Tetrahedron Lett. 1991, 32, 1847. Hartley, R. C.; Lamothe, S.; Chan, T. H. Tetrahedron Lett. 1993, 34, 1449.
16. Evans, D. A.; Andrews, G. C. Acc. Chem. Res. 1974, 7, 147. Mukaiyama, T.; Narasaka, K.; Maekawa, K.; Furusato, M. Bull. Chem. Soc. Jpn. 1971, 44, 2285.
17. Evans, D. A.; Andrews, G. C. Acc. Chem. Res. 1974, 7, 147. Mukaiyama, T.; Narasaka, K.; Maekawa, K.; Furusato, M. Bull. Chem. Soc. Jpn. 1971, 44, 2285.
18. (a) Jastrzebski, J. T. B. H.; van Koten, G.; Konijn, M.; Stam, C. H. J. Am. Chem. Soc. 1982, 104, 5490.
19. (b) Wehman, E.; Jastrzebski, J. T. B. H.; Ernsting. J.-M.; Grove, D. M.; van Koten, G. J, Organomet. Chem. 1988, 353, 145. Rietveld. M. H. P.: Wehman-Ooyevaar, I. C. M.; Kapteijn, G. M.: Grove, D. M.: Smeets, W. J. J.; Kooijman, H.; Spek, A. L.; van Koten, G. Organometallics 1994, 13, 3782.
20. (b) Wehman, E.; Jastrzebski, J. T. B. H.; Ernsting. J.-M.; Grove, D. M.; van Koten, G. J, Organomet. Chem. 1988, 353, 145. Rietveld. M. H. P.: Wehman-Ooyevaar, I. C. M.; Kapteijn, G. M.: Grove, D. M.: Smeets, W. J. J.; Kooijman, H.; Spek, A. L.; van Koten, G. Organometallics 1994, 13, 3782.
21. Harder, S.; Boersma, J.; Brandsma, L.; Kanters, J. A. J. Organomet. Chem. 1988, 339. 7.
22. (a) Harder, S.; Boersma, J.; Brandsma, L.; van Heteren, A.; Kanters, J. A.; Bauer, W.; Schleyer, P. von R. J. Am. Chem. Soc. 1988, 110, 7802.
23. (b) Sorger, K.; Schleyer, P. von R.; Stalke, D. J. Chem. Soc., Chem. Commun. 1995, 2279.
24. Jones, F. N.; Zinn, M. F.: Hauser, C. R. J. Org. Chem. 1963, 28, 663.
25. Grandjean, D.; Pale, P. Tetrahedron Lett. 1993, 34, 1155.
26. This solvent mixture is close in donor strength to THF and allows measurement of spectra to below -150 °C.
27. Lithium shifts are referenced to external 0.3 M LiCl in methanol.
28. We have not been able to assign B and C individually, since their predicted NMR properties are indentical. Attempts to make this distinction based on the effect of chelating solvents (in principle, C can chelate, B cannot) have not been successful. Evidence for across-ring chelation of this type in a tetramer has been reported: Bartlett, P. D.; Goebel, C. V.; Weber, W. P. J. Am. Chem. Soc. 1969, 91, 7425.
29. Jackman, L. M.; Scarmoutzos, L. M. J. Am. Chem. Soc. 1987, 109. 5348.
30. (a) Wanat, R. A.; Collum, D. B.; Van Duyne, G.; Clardy, J.; DePue, R. T. J. Am. Chem. Soc. 1986, 108, 3415.
31. (b) Collum, D. B. Ace. Chem. Res. 1993, 26, 227-234. Kallman, N.; Collum, D. B. J. Am. Chem. Soc. 1987, 109, 7466. Gilchrist, J. H.; Collum, D. B. J. Am. Chem. Soc. 1992, 114, 794.
32. (b) Collum, D. B. Ace. Chem. Res. 1993, 26, 227-234. Kallman, N.; Collum, D. B. J. Am. Chem. Soc. 1987, 109, 7466. Gilchrist, J. H.; Collum, D. B. J. Am. Chem. Soc. 1992, 114, 794.
33. (b) Collum, D. B. Ace. Chem. Res. 1993, 26, 227-234. Kallman, N.; Collum, D. B. J. Am. Chem. Soc. 1987, 109, 7466. Gilchrist, J. H.; Collum, D. B. J. Am. Chem. Soc. 1992, 114, 794.
34. (c) Collum, D. B. Acc. Chem. Res. 1992, 25, 448 and references therein.
35. 15,16a (18) Bauer, W.; Winchester, W. R.; Schleyer, P. v. R. Organometallics 1987, 6, 2371.
36. Particularly pertinent is the change in metalation site of p-(dimethylaminomethyl)anisole from ortho to the aminomethyl group to ortho to the methoxy group when TMEDA was present: Slocum, D. W.; Jennings, C. A. J. Org. Chem. 1976, 41, 3653.
37. (a) Katsoulos, G.; Takagishi, S.; Schlosser, M. Synlett 1991, 731. Barluenga, J.; Gonzalez, R.; Fañanás, J. Tetrahedron Lett. 1992, 33, 7573.
38. (a) Katsoulos, G.; Takagishi, S.; Schlosser, M. Synlett 1991, 731. Barluenga, J.; Gonzalez, R.; Fañanás, J. Tetrahedron Lett. 1992, 33, 7573.
39. 1d Fraenkel, G.; Chow, A.; Winchester, W. R. J. Am. Chem. Soc. 1990, 112, 6190.
40. 1d Fraenkel, G.; Chow, A.; Winchester, W. R. J. Am. Chem. Soc. 1990, 112, 6190.
41. 1d Fraenkel, G.; Chow, A.; Winchester, W. R. J. Am. Chem. Soc. 1990, 112, 6190.
42. Kaiser, E. M.; Thomas, W. R.; Synos, T. E.; McClure, J. R.; Mansour, T. S.; Garlich, J. R.; Chastain, J. E., Jr. J. Organomet. Chem. 1981, 213, 405. Fujisawa, T.; Nagai, M.; Koike, Y.; Shimizu, M. J. Org. Chem. 1994, 59, 5865.
43. Kaiser, E. M.; Thomas, W. R.; Synos, T. E.; McClure, J. R.; Mansour, T. S.; Garlich, J. R.; Chastain, J. E., Jr. J. Organomet. Chem. 1981, 213, 405. Fujisawa, T.; Nagai, M.; Koike, Y.; Shimizu, M. J. Org. Chem. 1994, 59, 5865.
44. 3, R = 0.0794 based on 3423 reflections, GOF = 1.027.
45. The complexation is 1:1. The competition between THF and TMEDA can be judged from the observation that half of the dimers A/B/C were converted to 3 at a ratio of [THF]/[TMEDA] of 60.