Structure and reactivity of lithium diisopropylamide solvated by polyamines: Evidence of monomer- and dimer-based dehydrohalogenations

Journal of the American Chemical Society

Volumn 120, Issue 17, 1998, Pages 4081-4086

  Remenar, Julius F ^a   Collum, David B ^a  

^a Department of Population Medicine and Diagnostic Sciences   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DIISOPROPYLAMINE; POLYAMINE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; HALOGENATION; SOLVATION;

EID: 0032490108     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9741279     Document Type: Article

References (42)

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4. Reviews of lithium amide structural studies: (a) Gregory, K.; Schleyer, P. v. R.; Snaith, R. Adv. Inorg. Chem. 1991, 37, 47. (b) Mulvey, R. E. Chem. Soc. Rev. 1991, 20, 167. (c) Collum, D. B. Acc. Chem. Res. 1993, 26, 227.
5. Collum, D. B. Acc. Chem. Res. 1993, 26, 227.
6. Lithium dialkylamides are important reagents in synthetic organic chemistry. For extensive leading references, see refs 7-10.
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16. For selected applications and mechanistic investigations of lithium amide-mediated 1,2-eliminations, see: (a) Mass, R. J.; Rickborn, B. J. Org. Chem. 1986, 51, 1992. (b) Kopka, I. E.; Nowak, M. A.; Rathke, M. W. Synth. Commun, 1986, 16, 27. (c) Evans, K. L.; Prince, P.; Huang, E. T.; Boss, K. R.; Gandour, R. D. Tetrahedron Lett. 1990, 31, 6753. (d) Reisdorf, D.; Normant, H. Organomet. Chem. Synth. 1972, 1, 375.
17. For selected applications and mechanistic investigations of lithium amide-mediated 1,2-eliminations, see: (a) Mass, R. J.; Rickborn, B. J. Org. Chem. 1986, 51, 1992. (b) Kopka, I. E.; Nowak, M. A.; Rathke, M. W. Synth. Commun, 1986, 16, 27. (c) Evans, K. L.; Prince, P.; Huang, E. T.; Boss, K. R.; Gandour, R. D. Tetrahedron Lett. 1990, 31, 6753. (d) Reisdorf, D.; Normant, H. Organomet. Chem. Synth. 1972, 1, 375.
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20. For extensive references to the chemistry of lithium amide open dimers, see ref 8.
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24. A's of carbon acids and amines have been studied previously: Fraser, R. R.; Mansour, T. S. J. Org. Chem. 1984, 49, 3442. Chevrot, C.; Perichon, J. Bull. Soc. Chem. Fr. 1977, 421, Bordwell, F. G.; Bartmess, J. E.; Drucker, G. E.; Margolin, Z.; Matthews, W. S. J. Am. Chem. Soc. 1975, 97, 3226. Streitwieser, A., Jr.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074. Streitwieser, A., Jr. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Eds.; Elsevier: New York, 1980; Chapter 7. Ahlbrecht, H.; Schneider, G. Tetrahedron 1986, 42, 4729. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S. Tetrahedron Lett. 1986, 27, 331. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S.; Savard, S. J. Org. Chem. 1985, 50, 3232. Fraser, R. R.; Bresse, M.; Mansour, T. S. J. Am. Chem. Soc. 1983, 705, 7790.
25. A's of carbon acids and amines have been studied previously: Fraser, R. R.; Mansour, T. S. J. Org. Chem. 1984, 49, 3442. Chevrot, C.; Perichon, J. Bull. Soc. Chem. Fr. 1977, 421, Bordwell, F. G.; Bartmess, J. E.; Drucker, G. E.; Margolin, Z.; Matthews, W. S. J. Am. Chem. Soc. 1975, 97, 3226. Streitwieser, A., Jr.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074. Streitwieser, A., Jr. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Eds.; Elsevier: New York, 1980; Chapter 7. Ahlbrecht, H.; Schneider, G. Tetrahedron 1986, 42, 4729. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S. Tetrahedron Lett. 1986, 27, 331. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S.; Savard, S. J. Org. Chem. 1985, 50, 3232. Fraser, R. R.; Bresse, M.; Mansour, T. S. J. Am. Chem. Soc. 1983, 705, 7790.
26. A's of carbon acids and amines have been studied previously: Fraser, R. R.; Mansour, T. S. J. Org. Chem. 1984, 49, 3442. Chevrot, C.; Perichon, J. Bull. Soc. Chem. Fr. 1977, 421, Bordwell, F. G.; Bartmess, J. E.; Drucker, G. E.; Margolin, Z.; Matthews, W. S. J. Am. Chem. Soc. 1975, 97, 3226. Streitwieser, A., Jr.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074. Streitwieser, A., Jr. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Eds.; Elsevier: New York, 1980; Chapter 7. Ahlbrecht, H.; Schneider, G. Tetrahedron 1986, 42, 4729. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S. Tetrahedron Lett. 1986, 27, 331. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S.; Savard, S. J. Org. Chem. 1985, 50, 3232. Fraser, R. R.; Bresse, M.; Mansour, T. S. J. Am. Chem. Soc. 1983, 705, 7790.
27. A's of carbon acids and amines have been studied previously: Fraser, R. R.; Mansour, T. S. J. Org. Chem. 1984, 49, 3442. Chevrot, C.; Perichon, J. Bull. Soc. Chem. Fr. 1977, 421, Bordwell, F. G.; Bartmess, J. E.; Drucker, G. E.; Margolin, Z.; Matthews, W. S. J. Am. Chem. Soc. 1975, 97, 3226. Streitwieser, A., Jr.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074. Streitwieser, A., Jr. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Eds.; Elsevier: New York, 1980; Chapter 7. Ahlbrecht, H.; Schneider, G. Tetrahedron 1986, 42, 4729. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S. Tetrahedron Lett. 1986, 27, 331. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S.; Savard, S. J. Org. Chem. 1985, 50, 3232. Fraser, R. R.; Bresse, M.; Mansour, T. S. J. Am. Chem. Soc. 1983, 705, 7790.
28. A's of carbon acids and amines have been studied previously: Fraser, R. R.; Mansour, T. S. J. Org. Chem. 1984, 49, 3442. Chevrot, C.; Perichon, J. Bull. Soc. Chem. Fr. 1977, 421, Bordwell, F. G.; Bartmess, J. E.; Drucker, G. E.; Margolin, Z.; Matthews, W. S. J. Am. Chem. Soc. 1975, 97, 3226. Streitwieser, A., Jr.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074. Streitwieser, A., Jr. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Eds.; Elsevier: New York, 1980; Chapter 7. Ahlbrecht, H.; Schneider, G. Tetrahedron 1986, 42, 4729. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S. Tetrahedron Lett. 1986, 27, 331. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S.; Savard, S. J. Org. Chem. 1985, 50, 3232. Fraser, R. R.; Bresse, M.; Mansour, T. S. J. Am. Chem. Soc. 1983, 705, 7790.
29. A's of carbon acids and amines have been studied previously: Fraser, R. R.; Mansour, T. S. J. Org. Chem. 1984, 49, 3442. Chevrot, C.; Perichon, J. Bull. Soc. Chem. Fr. 1977, 421, Bordwell, F. G.; Bartmess, J. E.; Drucker, G. E.; Margolin, Z.; Matthews, W. S. J. Am. Chem. Soc. 1975, 97, 3226. Streitwieser, A., Jr.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074. Streitwieser, A., Jr. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Eds.; Elsevier: New York, 1980; Chapter 7. Ahlbrecht, H.; Schneider, G. Tetrahedron 1986, 42, 4729. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S. Tetrahedron Lett. 1986, 27, 331. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S.; Savard, S. J. Org. Chem. 1985, 50, 3232. Fraser, R. R.; Bresse, M.; Mansour, T. S. J. Am. Chem. Soc. 1983, 705, 7790.
30. A's of carbon acids and amines have been studied previously: Fraser, R. R.; Mansour, T. S. J. Org. Chem. 1984, 49, 3442. Chevrot, C.; Perichon, J. Bull. Soc. Chem. Fr. 1977, 421, Bordwell, F. G.; Bartmess, J. E.; Drucker, G. E.; Margolin, Z.; Matthews, W. S. J. Am. Chem. Soc. 1975, 97, 3226. Streitwieser, A., Jr.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074. Streitwieser, A., Jr. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Eds.; Elsevier: New York, 1980; Chapter 7. Ahlbrecht, H.; Schneider, G. Tetrahedron 1986, 42, 4729. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S. Tetrahedron Lett. 1986, 27, 331. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S.; Savard, S. J. Org. Chem. 1985, 50, 3232. Fraser, R. R.; Bresse, M.; Mansour, T. S. J. Am. Chem. Soc. 1983, 705, 7790.
31. A's of carbon acids and amines have been studied previously: Fraser, R. R.; Mansour, T. S. J. Org. Chem. 1984, 49, 3442. Chevrot, C.; Perichon, J. Bull. Soc. Chem. Fr. 1977, 421, Bordwell, F. G.; Bartmess, J. E.; Drucker, G. E.; Margolin, Z.; Matthews, W. S. J. Am. Chem. Soc. 1975, 97, 3226. Streitwieser, A., Jr.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074. Streitwieser, A., Jr. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Eds.; Elsevier: New York, 1980; Chapter 7. Ahlbrecht, H.; Schneider, G. Tetrahedron 1986, 42, 4729. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S. Tetrahedron Lett. 1986, 27, 331. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S.; Savard, S. J. Org. Chem. 1985, 50, 3232. Fraser, R. R.; Bresse, M.; Mansour, T. S. J. Am. Chem. Soc. 1983, 705, 7790.
32. A's of carbon acids and amines have been studied previously: Fraser, R. R.; Mansour, T. S. J. Org. Chem. 1984, 49, 3442. Chevrot, C.; Perichon, J. Bull. Soc. Chem. Fr. 1977, 421, Bordwell, F. G.; Bartmess, J. E.; Drucker, G. E.; Margolin, Z.; Matthews, W. S. J. Am. Chem. Soc. 1975, 97, 3226. Streitwieser, A., Jr.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074. Streitwieser, A., Jr. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Eds.; Elsevier: New York, 1980; Chapter 7. Ahlbrecht, H.; Schneider, G. Tetrahedron 1986, 42, 4729. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S. Tetrahedron Lett. 1986, 27, 331. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S.; Savard, S. J. Org. Chem. 1985, 50, 3232. Fraser, R. R.; Bresse, M.; Mansour, T. S. J. Am. Chem. Soc. 1983, 705, 7790.
33. A's of carbon acids and amines have been studied previously: Fraser, R. R.; Mansour, T. S. J. Org. Chem. 1984, 49, 3442. Chevrot, C.; Perichon, J. Bull. Soc. Chem. Fr. 1977, 421, Bordwell, F. G.; Bartmess, J. E.; Drucker, G. E.; Margolin, Z.; Matthews, W. S. J. Am. Chem. Soc. 1975, 97, 3226. Streitwieser, A., Jr.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074. Streitwieser, A., Jr. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Eds.; Elsevier: New York, 1980; Chapter 7. Ahlbrecht, H.; Schneider, G. Tetrahedron 1986, 42, 4729. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S. Tetrahedron Lett. 1986, 27, 331. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S.; Savard, S. J. Org. Chem. 1985, 50, 3232. Fraser, R. R.; Bresse, M.; Mansour, T. S. J. Am. Chem. Soc. 1983, 705, 7790.
34. A's of carbon acids and amines have been studied previously: Fraser, R. R.; Mansour, T. S. J. Org. Chem. 1984, 49, 3442. Chevrot, C.; Perichon, J. Bull. Soc. Chem. Fr. 1977, 421, Bordwell, F. G.; Bartmess, J. E.; Drucker, G. E.; Margolin, Z.; Matthews, W. S. J. Am. Chem. Soc. 1975, 97, 3226. Streitwieser, A., Jr.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074. Streitwieser, A., Jr. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Eds.; Elsevier: New York, 1980; Chapter 7. Ahlbrecht, H.; Schneider, G. Tetrahedron 1986, 42, 4729. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S. Tetrahedron Lett. 1986, 27, 331. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7068. Fraser, R. R.; Mansour, T. S.; Savard, S. J. Org. Chem. 1985, 50, 3232. Fraser, R. R.; Bresse, M.; Mansour, T. S. J. Am. Chem. Soc. 1983, 705, 7790.
35. Fraenkel, G.; Martin, K. V. J. Am. Chem. Soc. 1995, 117, 10336.
36. 9
37. We generally find that lithium amide and other organolithium dynamic exchange processes observable by NMR spectroscopy are considerably faster in hexane than in toluene.
38. For an extensive bibliography and leading references to lithium amide mixed aggregation, see: Romesberg, F. E.; Collum, D. B. J. Am. Chem. Soc. 1994, 116, 9198.
39. Brown, H. C.; Krishnamurthy, S. J. Am. Chem. Soc. 1972, 94, 7159. Creary, X.; Hatoum, H. N.; Barton, A.; Aldridge, T. E. J. Org. Chem. 1992, 57, 1887. Bartsch, R. A.; Lee, J. G. J. Org. Chem. 1991, 56, 212.
40. Brown, H. C.; Krishnamurthy, S. J. Am. Chem. Soc. 1972, 94, 7159. Creary, X.; Hatoum, H. N.; Barton, A.; Aldridge, T. E. J. Org. Chem. 1992, 57, 1887. Bartsch, R. A.; Lee, J. G. J. Org. Chem. 1991, 56, 212.
41. Brown, H. C.; Krishnamurthy, S. J. Am. Chem. Soc. 1972, 94, 7159. Creary, X.; Hatoum, H. N.; Barton, A.; Aldridge, T. E. J. Org. Chem. 1992, 57, 1887. Bartsch, R. A.; Lee, J. G. J. Org. Chem. 1991, 56, 212.
42. n affords n = -0.74 ± 0.06. (See Figure 3.)