Multinuclear NMR study of the solution structure and reactivity of tris(trimethylsilyl)methyllithium and its iodine ate complex

Journal of Organic Chemistry

Volumn 74, Issue 2, 2009, Pages 719-729

  Reich, Hans J ^a   Sikorski, William H ^a   Sanders, Aaron W ^a   Jones, Amanda C ^a   Plessel, Kristin N ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ATE COMPLEXES; CONTACT ION PAIRS; DYNAMIC BEHAVIORS; DYNAMIC NMR; INTERCONVERSION; ION PAIRS; METHYL DERIVATIVES; METHYLLITHIUM; MULTI-NUCLEAR NMR; NATURAL ABUNDANCES; NMR CHEMICAL SHIFTS; RESTRICTED ROTATIONS; SOLUTION STRUCTURES; STERIC BULKS; TRIMETHYLSILYL; TRIMETHYLSILYL GROUPS;

AGGREGATES; INDUSTRIAL CHEMICALS; IODINE; NUCLEAR MAGNETIC RESONANCE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; ORGANIC SOLVENTS;

LITHIUM;

CARBON 13; DIMER; IODINE DERIVATIVE; MONOMER; RADIOISOTOPE; TRIMETHYLSILYL DERIVATIVE; BENZALDEHYDE; BENZALDEHYDE DERIVATIVE; DISULFIDE; ETHER DERIVATIVE; FURAN DERIVATIVE; IODINATED HYDROCARBON; IODINE; METHYL IODIDE; ORGANOMETALLIC COMPOUND; TRIS(TRIMETHYLSILYL)METHYLLITHIUM;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL REACTION; CHEMICAL STRUCTURE; NUCLEAR MAGNETIC RESONANCE; SOLUTION AND SOLUBILITY; CHEMISTRY; KINETICS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; TEMPERATURE;

BENZALDEHYDES; DISULFIDES; ETHERS; FURANS; HYDROCARBONS, IODINATED; IODINE; KINETICS; MAGNETIC RESONANCE SPECTROSCOPY; ORGANOMETALLIC COMPOUNDS; SOLUTIONS; TEMPERATURE; TRIMETHYLSILYL COMPOUNDS;

EID: 60849087363     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo802032d     Document Type: Article

References (76)

1. (a) For example, bis(tris(trimethylsilyl)methyl)-zinc can be steam distilled and does not react with either bromine or boiling concentrated hydrochloric acid. Eaborn, C.; Retta, N.; Smith, J. D. J. Organomet. Chem. 1980, 190, 101 106.
2. (b) Eaborn, C.; Smith, J. D. J. Chem. Soc, Dalton Trans. 2001, 1541 1552.
3. (c) Eaborn, C.; Hitchcock, P. B.; Smith, J. D.; Sullivan, A. C. J. Chem. Soc., Chem. Commun. 1983, 827-828.
4. (d) Buttrus, N. H.; Eaborn, C.; Hitchcock, P. B.; Smith, J. D.; Stamper, J. G.; Sullivan, A. C. J. Chem. Soc., Chem. Commun. 1986, 969-970.
5. (e) Avent, A. G.; Eaborn, C.; Hitchcock, P. B.; Lawless, G. A.; Lickiss, P. D.; Mallien, M.; Smith, J. D.; Webb, A. D.; Wrackmeyer, B. J. Chem. Soc., Dalton Trans. 1993, 3259-3264.
6. (f) Eaborn, C.; Clegg, W.; Hitchcock, P. B.; Hopman, M.; Izod, K.; O'Shaughnessy, P. N.; Smith, J. D. Organometallics 1997, 16, 4728-4736.
7. (a) Pepels, A.; Günther, H.; Amoureux, J. P.; Fernandez, C. J. Am. Chem. Soc. 2000, 122, 9858-9859.
8. Hiller, W.; Layh, M.; Uhl, W. Angew. Chem., Int. Ed. Engl. 1991, 30, 324-326.
9. (a) Reich, H. J.; Sikorski, W. H.; Gudmundsson, B. Odie;.; Dykstra, R. R. J. Am. Chem. Soc. 1998, 120, 4035-4036.
10. 13C NMR chemical shift thermometer: Sikorski, W. H.; Sanders, A. W.; Reich,
11. H. J. Magn. Resonan. Chem. 1998, 36, S118-S124.
12. (c) Reich, H. J.; Goldenberg, W. S.; Gudmundsson, B. O.; Sanders, A. W.; Kulicke, K. J.; Simon, K.; Guzei, I. A. J. Am. Chem. Soc. 2001, 123, 8067-8079.
13. (d) Jantzi, K. L.; Puckett, C. L.; Guzei, I. A.; Reich, H. J. J. Org. Chem. 2005, 70, 7520-7529.
14. (e) Reich, H. J.; Holladay, J. E.; Mason, J. D.; Sikorski, W. H. J. Am. Chem. Soc. 1995, 117, 12137-12150.
15. (f) Reich, H. J.; Goldenberg, W. S.; Sanders, A. W.; Jantzi, K. L.; Tzschucke, C. C. J. Am. Chem. Soc. 2003, 125, 3509-3521.
16. (g) Reich, H. J.; Borst, J. P.; Dykstra, R. R.; Green, D. P. J. Am. Chem. Soc. 1993, 115, 8728 8741.
17. (h) Reich, H. J.; Borst, J. P.; Dykstra, R. R. Tetrahedron 1994, 50, 5869 5880.
18. (i) Sikorski, W. H.; Reich, H. J. J. Am. Chem. Soc. 2001, 123, 6527 6535.
19. (j) Reich, H. J.; Dykstra, R. R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1469-1470.
20. (k) Reich, H. J.; Dykstra, R. R. J. Am. Chem. Soc. 1993,115, 7041 7042.
21. (l) Reich, H. J.; Green, D. P.; Medina, M. A.; Goldenberg, W. S.; Gudmundsson, B. O.; Dykstra, R. R.; Phillips, N. H. J. Am. Chem. Soc. 1998, 120, 7201-7210.
22. (m) Reich, H. J.; Holladay, J. E.; Walker, T. G.; Thompson, J. L. J. Am. Chem. Soc. 1999, 121, 9769-9780.
23. (n) Jones, A. C.; Sanders, A. W.; Bevan, M. J.; Reich, H. J. J. Am. Chem. Soc. 2007, 129, 3492-3493.
24. (o) Reich, H. J.; Green, D. P.; Phillips, N. H. J. Am. Chem. Soc. 1991, 113, 1414-1416.
25. (p) Reich, H. J.; Gudmundsson, B. O.; Green, D. P.; Bevan, M. J.; Reich, I. L. Helv. Chim. Acta 2002, 85, 3748-3772.
26. (q) Reich, H. J.; Phillips, N. H. Pure Appl. Chem. 1987, 59, 1021-1026.
27. (a) Reich, H. J.; Sikorski, W. H.; Thompson, J. L.; Sanders, A. W.; Jones, A. C. Org. Lett. 2006, 8, 4003-4006.
28. (b) Jones, A. C.; Sanders, A. W.; Sikorski, W. H.; Jansen, K. L.; Reich, H. J. J. Am. Chem. Soc. 2008, 130, 6060-6061.
29. (a) Bildmann, U. J.; Mueller, G. Organometallics 2001, 20, 1689-1691.
30. (b) Eiermann, M.; Hafner, K. J. Am. Chem. Soc. 1992, 114, 135.
31. (c) Harder, S.; Prosenc, M. H. Angew. Chem., Int. Ed. Engl. 1994, 33, 1744.
32. (d) Zaegel, F.; Gallucci, J. C.; Meunier, P.; Gautheron, B.; Sivik, M. R.; Paquette, L. A. J. Am. Chem. Soc. 1994, 116, 6466-6567.
33. (a) Fraenkel, G.; Hallden-Abberton, M. P. J. Am. Chem. Soc. 1981, 103, 5657-5664.
34. (b) Fraenkel, G.; Chow, A.; Winchester, W. R. J. Am. Chem. Soc. 1990, 112, 6190-6198.
35. (c) For an insightful discussion of dynamic processes involving C-Li multiplets in monomeric aryllithium reagents, see: Fraenkel, G.; Subramanian, S.; Chow, A. J. Am. Chem. Soc. 1995, 117, 6300-6307.
36. 7Li analogs show little or no quadrupolar broadening and thus couplings are more easily seen: Fraenkel, G.; Fraenkel, A. M.; Geckle, M. J.; Schloss, F. J. Am. Chem. Soc. 1979, 101, 4745-4747.
37. Hoic, D. A.; Davis, W. M.; Fu, G. C. J. Am. Chem. Soc. 1995, 117, 8480-8481.
38. (a) Romesberg, F. E.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5751-5757.
39. (b) Romesberg, F. E.; Bernstein, M. P.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1993, 115, 3475-3483.
40. (c) Galiano-Roth, A. S.; Collum, D. B. J. Am. Chem. Soc. 1988, 110, 3546-3553.
41. (d) Lucht, B. L.; Bernstein, M. P.; Remenar, J. F.; Collum, D. B. J. Am. Chem. Soc. 1996, 118, 10707-10718.
42. (a) Jackman, L. M.; Scarmoutzos, L. M.; Porter, W. J. Am. Chem. Soc. 1987, 109, 6524-6525.
43. (b) Jackman, L. M.; Scarmoutzos, L. M.; Smith, B. D.; Williard, P. G. J. Am. Chem. Soc. 1988, 110, 6058-6058.
44. Gornitzka, H.; Stalke, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 693 695.
45. (a) Cambillau, C.; Bram, G.; Corset, J.; Riche, C. Nouv. J. Chim. 1979, 3, 9-11.
46. (b) Cambillau, C.; Ourevitch, M. J. Chem. Soc., Chem. Commun. 1981, 996-997.
47. (c) Raban, M.; Haritos, D. P. J. Am. Chem. Soc. 1979, 101, 5178 5182.
48. (d) Teixidor, F.; Llobet, A.; Casabo, J.; Solans, X.; Font-Altaba, M.; Aguilo, M. Inorg. Chem. 1985, 24, 2315-2317.
49. (a) Bauer, W.; Seebach, D. Helv. Chim. Acta 1984, 67, 1972-1988.
50. (b) Seebach, D.; Hassig, R.; Gabriel, J. Helv. Chim. Acta 1983, 66, 308-337.
51. (c) Seebach, D.; Siegel, H.; Gabriel, J.; Hassig, R. Helv. Chim. Acta, 1980, 63, 2046-2053.
52. (a) Merker, R. L.; Scott, M. J. J. Organomet. Chem. 1965, 4, 98-100. (b) Guijarro, A.; Yus, M. T etrahedron 1996, 52, 1797-1810.
53. Casarini, D.; Foresti, E.; Lunazzi, L.; Mazzanti, A. Chem. -Eur. J. 1999, 5, 3501-3508.
54. Spectra and additional data are shown in the Supporting Information.
55. (a) Cahen, Y. M.; Dye, J. L.; Popov, A. I. J. Chem. Phys. 1975, 79, 1289-92.
56. (b) Cahen, Y. M.; Dye, J. L.; Popov, A. I. J. Phys. Chem. 1975, 79, 1292-1295.
57. (c) Shamsipur, M.; Popov, A. I. J. Phys. Chem. 1986, 90, 5997 5999.
58. Shamsipur, M.; Karkhaneei, E.; Afkhami, A. Polyhedron 1998, 17, 3809-3815.
59. Schade, S.; Boche, G. J. Organomet. Chem. 1998, 550, 381-395.
60. Rabideau, P. W.; Wetzel, D. M.; Husted, C. A.; Lawrence, J. R. Tetrahedron Lett. 1984, 25, 31-34.
61. Bauer, W.; Winchester, W. R.; Schleyer, P. v. R. Organometallics 1987, 6, 2371-2379.
62. Schümann, U.; Kopf, J.; Weiss, E. Angew. Chem. 1985, 97, 222. Schumann, U.; Kopf, J.; Weiss, E. Angew. Chem., Int. Ed. Engl. 1985, 24, 215 216.
63. Harder, S.; Boersma, J.; Brandsma, L.; van Mier, G. P. M.; Kanters, J. A. J. Organomet. Chem. 1989, 364, 1-15.
64. Bacon, J.; Gillespie, R. J.; Quail, J. W. Can. J. Chem. 1963, 41, 3063 3069.
65. Hartwell, G. E.; Allerhand, A. J. Am. Chem. Soc. 1971, 93, 4415-4418.
66. 4, MW7470 or 765 (depending on whether the
67. 8: Hamilton, D. G.; Crabtree, R. H. J. Am. Chem. Soc. 1988, 110, 4126-4133.
68. The barrier for interconversion of the SIP/CIP of lithium naphthalide in THF ether is G† = 3.5 kcal/mol at-50 °C: Hirota, N.; Carraway, R.; Schook, W. J. Am. Chem. Soc. 1968, 90, 3611-3618.
69. Jarek, R. L.; Miles, T. D.; Trester, M. L.; Denson, S. C.; Shin, S. K. J. Phys. Chem. A 2000, 104, 2230-2237.
70. Wittig, G.; Schollkopf, U. Tetrahedron 1958, 3, 91-93.
71. 3HgLi has not been fully published previously, and we include some NMR spectroscopic studies of HMPA titrations in Supporting Information.
72. Farnham, W. B.; Calabrese, J. C. J. Am. Chem. Soc. 1986, 108, 24492451.
73. Schulze, V.; Brönstrup, M.; Böhm, V. P. W.; Schwerdtfeger, P.; Schimeczek, M.; Hoffmann, R. W. Angew. Chem., Int. Ed. Engl. 1998, 37, 824 826.
74. Bailey, W. F.; Patricia, J. J. J. Organomet. Chem. 1988, 352, 1-46.
75. Chaplot, S. L.; Mclntyre, G. J.; Mierzejewski, A.; Pawley, G. S. Acta Crystallogr., Sect. B 1981, B37, 2210-2214.
76. Watson, S. C.; Eastham, J. F. J. Organomet. Chem. 1967, 9, 165-168.