Mechanistic studies of the lithium enolate of 4-fluoroacetophenone: Rapid-injection NMR study of enolate formation, dynamics, and aldol reactivity

Journal of the American Chemical Society

Volumn 133, Issue 42, 2011, Pages 16774-16777

  Kolonko, Kristopher J ^a   Wherritt, Daniel J ^a   Reich, Hans J ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALDOL REACTIONS; DIRECT REACTIONS; ENOLATES; EQUILIBRIUM STRUCTURES; HOMODIMERS; LITHIUM DIISOPROPYLAMIDE; LITHIUM ENOLATES; MECHANISTIC STUDIES; NMR STUDIES; SOLUTION CHEMISTRY; TETRAMERS;

ALDEHYDES; AMIDES; DIMERS;

LITHIUM;

4 FLUOROACETOPHENONE; DIMER; ELECTROPHILE; LITHIUM; LITHIUM ENOLATE; PYRROLIDINE DERIVATIVE; TETRAMER; UNCLASSIFIED DRUG;

ALDOL REACTION; ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL STRUCTURE; DISSOCIATION; FLUORINE NUCLEAR MAGNETIC RESONANCE; KINETICS; RAPID INJECTION NUCLEAR MAGNETIC RESONANCE; SUPRAMOLECULAR CHEMISTRY;

EID: 80054984612     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja207218f     Document Type: Article

References (47)

1. Bauer, W.; Seebach, D. Helv. Chim. Acta 1984, 67, 1972-1988
2. Amstutz, R.; Schweizer, W. B.; Seebach, D.; Dunitz, J. D. Helv. Chim. Acta 1981, 64, 2617-2621
3. Seebach, D.; Amstutz, R.; Dunitz, J. D. Helv. Chim. Acta 1981, 64, 2622-2626
4. Juaristi, E.; Beck, A. K.; Hansen, J.; Matt, T.; Mukhopadhyay, T.; Simson, M.; Seebach, D. Synthesis 1993, 1271-1290
5. Arnett, E. M.; Moe, K. D. J. Am. Chem. Soc. 1991, 113, 7288-7293
6. Arnett, E. M.; Fisher, F. J.; Nichols, M. A.; Ribeiro, A. A. J. Am. Chem. Soc. 1989, 111, 748-749
7. Arnett, E. M.; Fisher, F. J.; Nichols, M. A.; Ribeiro, A. A. J. Am. Chem. Soc. 1990, 112, 801-808
8. Arnett, E. M.; Palmer, C. A. J. Am. Chem. Soc. 1990, 112, 7354-7360
9. A brief RI-NMR study of the aldol reaction of lithium pinacolate (intended mainly to rule out SET mechanisms) is the only kinetic study we are aware of: Palmer, C. A.; Ogle, C. A.; Arnett, E. M. J. Am. Chem. Soc. 1992, 114, 5619-5625
10. Wang, D. Z. R.; Kim, Y.-J.; Streitwieser, A. J. Am. Chem. Soc. 2000, 122, 10754-10760
11. Kim, Y.-J.; Streitwieser, A. Org. Lett. 2002, 4, 573-575
12. The monomer of p -phenylisobutyrophenone lithium enolate is 2700 times as reactive as the dimer in an alkylation reaction: Abu-Hasanayn, F.; Streitwieser, A. J. Am. Chem. Soc. 1996, 118, 8136-8137
13. Streitwieser, A.; Leung, S. S.-W.; Kim, Y.-J. Org. Lett. 1999, 1, 145-147
14. Gruver, J. M.; Liou, L. R.; McNeil, A. J.; Ramirez, A.; Collum, D. B. J. Org. Chem. 2008, 73, 7743-7747
15. Liou, L. R.; McNeil, A. J.; Ramirez, A.; Toombes, G. E. S.; Gruver, J. M.; Collum, D. B. J. Am. Chem. Soc. 2008, 130, 4859-4868
16. Sun, X. F.; Kenkre, S. L.; Remenar, J. F.; Gilchrist, J. H.; Collum, D. B. J. Am. Chem. Soc. 1997, 119, 4765-4766
17. Hall, P. L.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 9575
18. 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, 5053-5055
19. Sun, X.; Collum, D. B. J. Am. Chem. Soc. 2000, 122, 2459-2463
20. Remenar, J. F.; Lucht, B. L.; Collum, D. B. J. Am. Chem. Soc. 1997, 119, 5567-5572
21. Ramirez, A.; Sun, X.; Collum, D. B. J. Am. Chem. Soc. 2006, 128, 10326-10336
22. Collum, D. B.; McNeil, A. J.; Ramirez, A. Angew. Chem., Int. Ed. 2007, 46, 3002-3017
23. Remenar, J. F.; Lucht, B. L.; Kruglyak, D.; Romesberg, F. E.; Gilchrist, J. H.; Collum, D. B. J. Org. Chem. 1997, 62, 5748-5754
24. Hoepker, A. C.; Gupta, L.; Ma, Y.; Faggin, M. F.; Collum, D. B. J. Am. Chem. Soc. 2011, 133, 7135-7151
25. Kolonko, K. J.; Biddle, M. M.; Guzei, I. A.; Reich, H. J. J. Am. Chem. Soc. 2009, 131, 11525-11534
26. Kolonko, K. J.; Guzei, I. A.; Reich, H. J. J. Org. Chem. 2010, 75, 6163-6172
27. The DNMR simulations were performed with an updated version of WINDNMR (http://www.chem.wisc.edu/areas/reich/plt/windnmr.htm).
28. Reich, H. J. J. Chem. Educ. 1995, 72, 1086
29. Reich, H. J. " WinDNMR Dynamic NMR Spectra for Windows ", J. Chem. Ed. Software, Series D 1996, 3D, 17-19, 27-33, 56-66.
30. Jones, A. C.; Sanders, A. W.; Bevan, M. J.; Reich, H. J. J. Am. Chem. Soc. 2007, 129, 3492-3493
31. Kolonko, K. J.; Reich, H. J. J. Am. Chem. Soc. 2008, 130, 9668-9669
32. The graph includes a point for the monomeric TMTAN complex of 1-Li, prepared at -115 °C by deprotonation of 1-H by the monomeric TMTAN complex of lithium tetramethylpiperidide. (4j) We will report on this separately but include the datum here to illustrate the remarkable consistency of the chemical shift effect.
33. +) towards MeI at -131°C: Jones, A. C.; Sanders, A. W.; Sikorski, W. H.; Jansen, K. L.; Reich, H. J. J. Am. Chem. Soc. 2008, 130, 6060-6061
34. The 2-lithiothiophene monomer is >1000 times as reactive as the dimer in the lithium-iodine exchange reaction at -102 °C: Reich, H. J; Whipple, W. L. Can. J. Chem. 2005, 83, 1577-1587
35. - = 0.02 (Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165-195)
36. a (DMSO) values of 1-H and 2-H are 24.5 and 24.7, respectively (Bordwell, F. G.; Cornforth, F. J. J. Org. Chem. 1978, 43, 1763-1768)
37. For an interesting example using the dynamics of lithium enolate heteroaggregate formation as a mechanistic probe, see: Casey, B. M.; Flowers, R. A., II. J. Am. Chem. Soc. 2011, 133, 11492-11495
38. Xie, L.; Saunders, W. H. J. Am. Chem. Soc. 1991, 113, 3123-3130
39. Held, G.; Xie, L. Microchem. J. 1997, 55, 261-269
40. Lecachey, B.; Duguet, N.; Oulyadi, H.; Fressigné, C.; Harrison-Marchand, A.; Yamamoto, Y.; Tomioka, K.; Maddaluno, J. Org. Lett. 2009, 11, 1907-1910
41. Henderson, K. W.; Dorigo, A. E.; Liu, Q.-Y.; Williard, P. G.; Schleyer, P. v. R.; Bernstein, P. R. J. Am. Chem. Soc. 1996, 118, 1339-1347
42. Williard, P. G.; Hintze, M. J. J. Am. Chem. Soc. 1990, 112, 8602-8604
43. Li, D.; Sun, C.; Williard, P. G. J. Am. Chem. Soc. 2008, 130, 11726-11736
44. Williard, P. G.; Salvino, J. M. Tetrahedron Lett. 1985, 26, 3931-3934
45. Pratt, L. M.; Streitwieser, A. J. Org. Chem. 2003, 68, 2830-2838
46. COmplex PAthway SImulator. Hoops, S.; Sahle, S.; Gauges, R.; Lee, C.; Pahle, J.; Simus, N.; Singhal, M.; Xu, L.; Mendes, P.; Kummer, U. Bioinformatics 2006, 22, 3067-3074
47. 4 faster: Das, G.; Thornton, E. R. J. Am. Chem. Soc. 1993, 115, 1302-1312