Solution structure of lithium dicyclohexylamide (Cy2NLi) and related mixed aggregates: Comparison with lithium diisopropylamide

Journal of Organic Chemistry

Volumn 61, Issue 24, 1996, Pages 8674-8676

  Aubrecht, Katherine B ^a   Collum, David B ^a  

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

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000550273     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo961084q     Document Type: Article

References (26)

1. d'Angelo, J. Tetrahedron 1976, 32, 2979. Heathcock, C. H. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Ed.; Elsevier: New York, 1980; Vol. B, Chapter 4. Cox, P. J.; Simpkins, N. S. Tetrahedron: Asymmetry 1991, 2, 1. Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1983; Vols. 2 and 3. Evans, D. A. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1983; Vol. 3, Chapter 1. Snieckus, V. Chem. Rev. 1990, 90, 879.
2. d'Angelo, J. Tetrahedron 1976, 32, 2979. Heathcock, C. H. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Ed.; Elsevier: New York, 1980; Vol. B, Chapter 4. Cox, P. J.; Simpkins, N. S. Tetrahedron: Asymmetry 1991, 2, 1. Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1983; Vols. 2 and 3. Evans, D. A. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1983; Vol. 3, Chapter 1. Snieckus, V. Chem. Rev. 1990, 90, 879.
3. d'Angelo, J. Tetrahedron 1976, 32, 2979. Heathcock, C. H. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Ed.; Elsevier: New York, 1980; Vol. B, Chapter 4. Cox, P. J.; Simpkins, N. S. Tetrahedron: Asymmetry 1991, 2, 1. Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1983; Vols. 2 and 3. Evans, D. A. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1983; Vol. 3, Chapter 1. Snieckus, V. Chem. Rev. 1990, 90, 879.
4. d'Angelo, J. Tetrahedron 1976, 32, 2979. Heathcock, C. H. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Ed.; Elsevier: New York, 1980; Vol. B, Chapter 4. Cox, P. J.; Simpkins, N. S. Tetrahedron: Asymmetry 1991, 2, 1. Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1983; Vols. 2 and 3. Evans, D. A. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1983; Vol. 3, Chapter 1. Snieckus, V. Chem. Rev. 1990, 90, 879.
5. d'Angelo, J. Tetrahedron 1976, 32, 2979. Heathcock, C. H. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Ed.; Elsevier: New York, 1980; Vol. B, Chapter 4. Cox, P. J.; Simpkins, N. S. Tetrahedron: Asymmetry 1991, 2, 1. Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1983; Vols. 2 and 3. Evans, D. A. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1983; Vol. 3, Chapter 1. Snieckus, V. Chem. Rev. 1990, 90, 879.
6. d'Angelo, J. Tetrahedron 1976, 32, 2979. Heathcock, C. H. In Comprehensive Carbanion Chemistry; Buncel, E., Durst, T., Ed.; Elsevier: New York, 1980; Vol. B, Chapter 4. Cox, P. J.; Simpkins, N. S. Tetrahedron: Asymmetry 1991, 2, 1. Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1983; Vols. 2 and 3. Evans, D. A. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1983; Vol. 3, Chapter 1. Snieckus, V. Chem. Rev. 1990, 90, 879.
7. Collum, D. B. Acc. Chem. Res. 1993, 26, 227.
8. Davidson, M. G.; Snaith, R.; Stalke, D.; Wright, D. S. J. Org. Chem. 1993, 58, 2810. Reed, D.; Barr, D.; Mulvey, R. E.; Snaith, R. J. Chem. Soc., Dalton Trans. 1986, 557.
9. Davidson, M. G.; Snaith, R.; Stalke, D.; Wright, D. S. J. Org. Chem. 1993, 58, 2810. Reed, D.; Barr, D.; Mulvey, R. E.; Snaith, R. J. Chem. Soc., Dalton Trans. 1986, 557.
10. 2NLi, see: Jubb, J.; Berno, P.; Hao, S.; Gambarotta, S. Inorg. Chem. 1995, 34, 3563.
11. 15N NMR spectroscopic investigations of LDA, see: (a) Galiano-Roth, A. S.; Collum, D. B. J. Am. Chem. Soc. 1989, 111, 6772. (b) Romesberg, F. E.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5751. (c) Galiano-Roth, A. S.; Kim, Y.-J.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5053. (d) Kim, Y.-J.; Bernstein, M. P.; Galiano-Roth, A. S.; Romesberg, F. E.; Williard, P. G.; Fuller, D. J.; Harrison, A. T.; Collum, D. B. J. Org. Chem. 1991, 56, 4435. (e) Romesberg, F. E.; Collum, D. B. J. Am. Chem. Soc. 1994, 116, 9198. (f) Kim, Y.-J.; Bernstein, M. P.; Galiano-Roth, A. S.; Romesberg, F. E.; Williard, P. G.; Fuller, D. J.; Harrison, A. T.; Collum, D. B. J. Org. Chem. 1991, 56, 4435.
12. 15N NMR spectroscopic investigations of LDA, see: (a) Galiano-Roth, A. S.; Collum, D. B. J. Am. Chem. Soc. 1989, 111, 6772. (b) Romesberg, F. E.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5751. (c) Galiano-Roth, A. S.; Kim, Y.-J.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5053. (d) Kim, Y.-J.; Bernstein, M. P.; Galiano-Roth, A. S.; Romesberg, F. E.; Williard, P. G.; Fuller, D. J.; Harrison, A. T.; Collum, D. B. J. Org. Chem. 1991, 56, 4435. (e) Romesberg, F. E.; Collum, D. B. J. Am. Chem. Soc. 1994, 116, 9198. (f) Kim, Y.-J.; Bernstein, M. P.; Galiano-Roth, A. S.; Romesberg, F. E.; Williard, P. G.; Fuller, D. J.; Harrison, A. T.; Collum, D. B. J. Org. Chem. 1991, 56, 4435.
13. 15N NMR spectroscopic investigations of LDA, see: (a) Galiano-Roth, A. S.; Collum, D. B. J. Am. Chem. Soc. 1989, 111, 6772. (b) Romesberg, F. E.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5751. (c) Galiano-Roth, A. S.; Kim, Y.-J.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5053. (d) Kim, Y.-J.; Bernstein, M. P.; Galiano-Roth, A. S.; Romesberg, F. E.; Williard, P. G.; Fuller, D. J.; Harrison, A. T.; Collum, D. B. J. Org. Chem. 1991, 56, 4435. (e) Romesberg, F. E.; Collum, D. B. J. Am. Chem. Soc. 1994, 116, 9198. (f) Kim, Y.-J.; Bernstein, M. P.; Galiano-Roth, A. S.; Romesberg, F. E.; Williard, P. G.; Fuller, D. J.; Harrison, A. T.; Collum, D. B. J. Org. Chem. 1991, 56, 4435.
14. 15N NMR spectroscopic investigations of LDA, see: (a) Galiano-Roth, A. S.; Collum, D. B. J. Am. Chem. Soc. 1989, 111, 6772. (b) Romesberg, F. E.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5751. (c) Galiano-Roth, A. S.; Kim, Y.-J.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5053. (d) Kim, Y.-J.; Bernstein, M. P.; Galiano-Roth, A. S.; Romesberg, F. E.; Williard, P. G.; Fuller, D. J.; Harrison, A. T.; Collum, D. B. J. Org. Chem. 1991, 56, 4435. (e) Romesberg, F. E.; Collum, D. B. J. Am. Chem. Soc. 1994, 116, 9198. (f) Kim, Y.-J.; Bernstein, M. P.; Galiano-Roth, A. S.; Romesberg, F. E.; Williard, P. G.; Fuller, D. J.; Harrison, A. T.; Collum, D. B. J. Org. Chem. 1991, 56, 4435.
15. 15N NMR spectroscopic investigations of LDA, see: (a) Galiano-Roth, A. S.; Collum, D. B. J. Am. Chem. Soc. 1989, 111, 6772. (b) Romesberg, F. E.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5751. (c) Galiano-Roth, A. S.; Kim, Y.-J.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5053. (d) Kim, Y.-J.; Bernstein, M. P.; Galiano-Roth, A. S.; Romesberg, F. E.; Williard, P. G.; Fuller, D. J.; Harrison, A. T.; Collum, D. B. J. Org. Chem. 1991, 56, 4435. (e) Romesberg, F. E.; Collum, D. B. J. Am. Chem. Soc. 1994, 116, 9198. (f) Kim, Y.-J.; Bernstein, M. P.; Galiano-Roth, A. S.; Romesberg, F. E.; Williard, P. G.; Fuller, D. J.; Harrison, A. T.; Collum, D. B. J. Org. Chem. 1991, 56, 4435.
16. 15N NMR spectroscopic investigations of LDA, see: (a) Galiano-Roth, A. S.; Collum, D. B. J. Am. Chem. Soc. 1989, 111, 6772. (b) Romesberg, F. E.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5751. (c) Galiano-Roth, A. S.; Kim, Y.-J.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5053. (d) Kim, Y.-J.; Bernstein, M. P.; Galiano-Roth, A. S.; Romesberg, F. E.; Williard, P. G.; Fuller, D. J.; Harrison, A. T.; Collum, D. B. J. Org. Chem. 1991, 56, 4435. (e) Romesberg, F. E.; Collum, D. B. J. Am. Chem. Soc. 1994, 116, 9198. (f) Kim, Y.-J.; Bernstein, M. P.; Galiano-Roth, A. S.; Romesberg, F. E.; Williard, P. G.; Fuller, D. J.; Harrison, A. T.; Collum, D. B. J. Org. Chem. 1991, 56, 4435.
17. Gilchrist, J. H.; Collum, D. B. J. Am. Chem, Soc. 1992, 114, 794.
18. 6Li resonances at -125°C (δ 2.08 and 1.67 ppm) suggesting the presence of a mixed solvated dimer bearing one HMPA. The rapid exchange precluded detailed investigation.
19. 2Li.
20. 2NLi in hydrocarbons with trans-N,N,N′,N′-tetramethylcyclohexanediamine (TMCDA) affords the TMCDA-solvated monomers, both with coupling constants of 10.1 Hz. Remenar, J. F.; Collum, D. B. Unpublished results. Details will be reported in due course.
21. 15N coupling, see: Koizumi, T.; Morihashi, K.; Kikuchi, O. Bull. Chem. Soc. Jpn. 1996, 69, 305.
22. 15N resonance correlations were confirmed by single frequency irradiations: Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1990, 112, 4069.
23. 2NH to CyNLi/HMPA in benzene provided the mixed aggregate along with several other resonances, leaving us unsure of the nature of the decomposition and the resulting mixed aggregate structure.
24. Kaiser, E. M.; Petty, J. D.; Solter, L. E. J. Organomet. Chem. 1973, 61, C1. Nadler, E. B.; Zipory, E. S.; Rappoport, Z. J. Org. Chem. 1991, 56, 4241. Magnus, P.; Roy, G. Synthesis 1980, 575.
25. Kaiser, E. M.; Petty, J. D.; Solter, L. E. J. Organomet. Chem. 1973, 61, C1. Nadler, E. B.; Zipory, E. S.; Rappoport, Z. J. Org. Chem. 1991, 56, 4241. Magnus, P.; Roy, G. Synthesis 1980, 575.
26. Kaiser, E. M.; Petty, J. D.; Solter, L. E. J. Organomet. Chem. 1973, 61, C1. Nadler, E. B.; Zipory, E. S.; Rappoport, Z. J. Org. Chem. 1991, 56, 4241. Magnus, P.; Roy, G. Synthesis 1980, 575.