Lithium diisopropylamide-mediated reactions of imines, unsaturated esters, epoxides, and aryl carbamates: Influence of hexamethylphosphoramide and ethereal cosolvents on reaction mechanisms

Journal of the American Chemical Society

Volumn 129, Issue 47, 2007, Pages 14818-14825

  Ma, Yun ^a   Collum, David B ^a  

^a Department of Obstetrics Gynecology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; CHEMICAL REACTIVITY; DIMERS; ESTERS; LITHIUM COMPOUNDS; SOLVENTS;

HEXAMETHYLPHOSPHORAMIDE; LITHIUM DIISOPROPYLAMIDE; MECHANISTIC COMPLEXITY;

AMIDES;

CARBAMIC ACID DERIVATIVE; EPOXIDE; ESTER; HEMPA; IMINE; LITHIUM;

ARTICLE; CONJUGATION; LITHIATION; PROTON TRANSPORT; REACTION ANALYSIS; SOLVATION;

AMIDES; CARBAMATES; EPOXY COMPOUNDS; ESTERS; IMINES; LITHIUM COMPOUNDS; MAGNETIC RESONANCE SPECTROSCOPY; METHYLATION; MOLECULAR STRUCTURE; PHOSPHORUS; SOLVENTS;

EID: 36749006077     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja074554e     Document Type: Article

References (112)

1. (a) Dykstra, R. R. In Encyclopedia of Reagents for Organic Synthesis; Paquette, L. A., Ed.; Wiley: New York, 1995; Vol. 4, p 2668.
2. (b) For a particularly interesting survey of stereo- and regioselectivity affiliated with organolithium chemistry, see: Clayden, J. Organolithiums; Selectivity for Synthesis; Pergamon: New York, 2002.
3. (a) Reich, H. J.; Kulicke, K. J. J. Am. Chem. Soc. 1995, 117, 6621.
4. (b) Reich, H. J.; Green, D. P.; Medina, M. A.; Goldenberg, W. J.; Gudmundsson, B. Ö.; Dykstra, R. R.; Philips, N. H. J. Am. Chem. Soc. 1998, 120, 7201.
5. (c) Reich, H. J.; Sikorski, W. H.; Gudmundsson, B. Ö.; Dykstra, R. R. J. Am. Chem. Soc. 1998, 120, 4035.
6. (d) Reich, H. J.; Holladay, J. A.; Mason, J. D.; Sikorski, W. H. J. Am. Chem. Soc. 1995, 117, 12137.
7. (e) Reich, H. J.; Borst, J. P.; Dykstra, R. R.; Green, D. P. J. Am. Chem. Soc. 1993, 115, 8728.
8. (f) Jantzi, K. L.; Puckett, C. L.; Guzei, I. A.; Reich, H. J. J. Org. Chem. 2005, 70, 7520 and references cited therein.
9. Leading references: (a) Reich, H. J.; Sanders, A. W.; Fiedler, A. T.; Bevan, M. J. J. Am. Chem. Soc. 2002, 124, 13386.
10. (b) Reich, H. J.; Green, D. P.; Phillips, N. H. J. Am. Chem. Soc. 1989, 111, 3444.
11. (c) Reich, H. J.; Phillips, N. H.; Reich, I. L. J. Am. Chem. Soc. 1985, 107, 4101.
12. (d) Reich, H. J.; Dykstra, R. R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1469.
13. (e) Reich, H. J.; Sikorski, W. H. J. Org. Chem. 1999, 64, 14.
14. (a) Sun, X.; Kenkre, S. L.; Remenar, J. F.; Gilchrist, J. H.; Collum, D. B. J. Am. Chem. Soc. 1997, 119, 4765.
15. (b) Sun, X.; Collum, D. B. J. Am. Chem. Soc. 2000, 122, 2452.
16. (c) Sun, X.; Collum, D. B. J. Am. Chem. Soc. 2000, 122, 2459.
17. Ma, Y.; Ramirez, A.; Singh, K. J.; Keresztes, I.; Collum, D. B. J. Am. Chem. Soc. 2006, 128, 15399.
18. (a) Romesberg, F. E.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. J. Am. Chem. Soc. 1991, 113, 5751.
19. (b) Romesberg, F. E.; Collum, D. B. J. Am. Chem. Soc. 1994, 116, 9198. Also, see ref 4.
20. (a) Romesberg, F. E.; Collum, D. B. J. Am. Chem. Soc. 1992, 114, 2112.
21. (b) Armstrong, D. R.; Mulvey, R. E.; Walker, G. T.; Barr, D.; Snaith, R.; Clegg, W.; Reed, D. J. Chem. Soc., Dalton Trans. 1988, 617.
22. (c) Armstrong, D. R.; Barr, D.; Brooker, A. T.; Clegg, W.; Gregory, K.; Hodgson, S. M.; Snaith, R.; Wright, D. S. Angew. Chem., Int. Ed. Engl 1990, 102, 443.
23. (d) Romesberg, F. E.; Collum, D. B. J. Am. Chem. Soc. 1992, 114, 2112.
24. (e) Romesberg, F. E.; Collum, D. B. J. Am. Chem. Soc. 1994, 116, 9187.
25. (f) Romesberg, F. E.; Collum, D. B. J. Am. Chem. Soc. 1995, 117, 2166.
26. (a) Ramirez, A.; Lobkovsky, E.; Collum, D. B. J. Am. Chem. Soc. 2003, 125, 15376.
27. (b) Liao, S.; Collum, D. B. J. Am. Chem. Soc. 2003, 125, 15114.
28. (c) Pratt, L.; Robbins, S. J. Mol. Struct. (THEOCHEM) 1999, 466, 95.
29. (a) Ramirez, A.; Collum, D. B. J. Am. Chem. Soc. 1999, 121, 11114.
30. (b) Wiedemann, S. H.; Ramirez, A.; Collum, D. B. J. Am. Chem. Soc. 2003, 125, 15893.
31. (c) Remenar, J. F.; Collum, D. B. J. Am. Chem. Soc. 1997, 119, 5573.
32. For an incisive review of lithium amides in organic synthesis, see: Eames, J. Product Subclass 6: Lithium Amides. In Science of Synthesis; Snieckus, V., Ed.; Thieme: New York, 2006; Vol. 8a, p 173.
33. Bernstein, M. P.; Collum, D. B. J. Am. Chem. Soc. 1993, 115, 8008.
34. For leading references to the organolithium chemistry of imines, see: Meyers, A. I. J. Org. Chem. 2005, 70, 6137.
35. (a) Herrman, J. L.; Kieczykowski, G. R.; Schlessinger, R. H. Tetrahedron Lett. 1973, 2433.
36. (b) Uyehara, T.; Asao, N.; Yamamoto, Y. J. Chem. Soc. Chem. Commun. 1987, 1410.
37. (c) Bellasoued, M.; Ennigrou, R.; Gaudemar, M. J. Organomet. Chem. 1988, 338, 149.
38. Davies, S. G.; Smith, A. D.; Price, P. D. Tetrahedron: Asymmetry 2005, 16, 2833.
39. (a) Satoh, T. Chem. Rev. 1996, 96, 3303.
40. (b) Crandall, J. K.; Apparu, M. Org. React. 1983, 29, 345.
41. (c) Magnus, A.; Bertilsson, S. K.; Andersson, P. G. Chem. Soc. Rev. 2002, 31, 223.
42. (d) Hodgson, D. M.; Gras, E. Synthesis 2002, 1625.
43. (e) Hodgson, D. M.; Chung, Y. K.; Nuzzo, I.; Freixas, G.; Kulikiewicz, K. K.; Cleator, E.; Paris, J.-M. J. Am. Chem. Soc. 2007, 129, 4456.
44. (f) Yanagisawa, A.; Yasue, K.; Yamamoto, H. J. Chem. Soc. Chem. Commun. 1994, 2103.
45. (g) Chemla, F.; Vrancken, E. In The Chemistry of Organolithium Compounds: Rappoport, Z., Marek, I., Eds.; Wiley: New York, 2004; Vol. 2, Chapter 18.
46. (a) Morgan, K. M.; Gronert, S. J. Org. Chem. 2000, 65, 1461.
47. (b) Morgan, K. M.; Gajewski, J. J. J. Org. Chem. 1996, 61, 820.
48. (c) Crandall, J. K.; Crawley, L. C.; Banks, D. B.; Lin, L. J. Org. Chem. 1971, 36, 510.
49. (d) Thummel, R. P.; Rickborn, B. J. Am. Chem. Soc. 1970, 92, 2064.
50. (e) Cope, A. C.; Berchtold, G. A.; Peterson, P. E.; Sharman, S. H. J. Am. Chem. Soc. 1960, 82, 6370.
51. (f) Gronert, S.; Lee, J. M. J. Org. Chem. 1995, 60, 448.
52. The mechanisms of epoxide metalations by chiral lithium amides have been studied extensively: (a) Pettersen, D.; Diner, P.; Amedjkouh, M.; Ahlberg, Per. I. Tetrahedron: Asymmetry 2004, 15, 1607.
53. (b) Yoshida, T.; Sakakibara, K.; Asami, M. Chem. Lett. 2003, 32, 150.
54. (c) Arvidsson, Per, I.; Hilmersson, G.; Davidsson, O. Helv. Chim. Acta 2002, 85, 3814.
55. (d) Pettersen, D.; Amedjkouh, M.; Lill, S. O. N.; Dahlen, K.; Ahlberg, Per. I. J. Chem. Soc., Perkin Trans. 2 2001, 9, 1654.
56. (e) Hilmersson, G.; Malmros, B. Chem. Eur. - J. 2001, 7, 337.
57. (f) Olsson, R. I.; Ahlberg, Per. I. Tetrahedron: Asymmetry 1999, 10, 3991.
58. (a) Hartung, C. G.; Snieckus, V. In Modern Arene Chemistry; Astruc, D., Ed.; Wiley-VCH: Weinheim, 2002; Chapter 10.
59. (b) Snieckus, V. Chem. Rev. 1990, 90, 879.
60. (c) Taylor, C. M.; Watson, A. J. Curr. Org. Chem. 2004, 8, 623.
61. For a review of rates studies of LDA-mediated reactions, see: Collum, D. B.; McNeil, A. J.; Ramirez, A. Angew. Chem., Int. Ed. 2007, 49, 3002.
62. Edwards, J. O.; Greene, E. F.; Ross, J. J. Chem. Educ. 1968, 45, 381.
63. For reviews of structural studies of N-lithiated species, see: (a) Collum, D. B. Acc. Chem. Res. 1993, 26, 227.
64. (b) Gregory, K.; Schleyer, P. v. R.; Snaith, R. Adv. Inorg. Chem. 1991, 37, 47.
65. (c) Mulvey, R. E. Chem. Soc. Rev. 1991, 20, 167.
66. (d) Lucht, B. L.; Collum, D. B. Acc. Chem. Res. 1999, 32, 1035.
67. For discussions of solvent - solvent interactions in solutions of HMPA, see: (a) Masaguer, J. R.; Casas, J. S.; Sousa Fernandez, A.; Sordo, J. An. Quim. 1973, 69, 199.
68. (b) Michou-Saucet, M. A.; Jose, J.; Michou-Saucet, C.; Merlin, J. C. Thermochim. Acta 1984, 75, 85.
69. (c) Vandyshev, V. N.; Serebryakova, A. L. Russ. J. Gen. Chem. 1997, 67, 540.
70. (d) Kulikov, M. V. Russ. Chem. Bull. 1997, 46, 274.
71. (e) Mehta, S. K.; Sharma, A. K.; Bhasin, K. K.; Parkash, R. Fluid Phase Equilib. 2002, 201, 203.
72. (f) Izutsu, K.; Kobayashi, N. J. Electroanal. Chem. 2005, 574, 197.
73. (g) Prado-Gotor, R.; Ayala, A.; Tejeda, A. B.; Suarez, M. B.; Mariscal, C.; Sanchez, M. D.; Hierro, G.; Lama, A.; Aldea, A.; Jimenez, R. Int. J. Chem. Kinet. 2003, 35, 361.
74. (h) Salomon, M. J. Power Sources 1989, 26, 9.
75. (a) Lucht, B. L.; Collum, D. B. J. Am. Chem. Soc. 1996, 118, 2217.
76. (b) Lucht, B. L.; Bernstein, M. P.; Remenar, J. F.; Collum, D. B. J. Am. Chem. Soc. 1996, 118, 10707.
77. (c) Reimers, J. R.; Hall, L. E. J. Am. Chem. Soc. 1999, 121, 3730.
78. (d) Wu, S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1996, 118, 715.
79. (e) Chadwick, S. T.; Rennels, R. A.; Rutherford, J. L.; Collum, D. B. J. Am. Chem. Soc. 2000, 122, 8640.
80. (f) Lewis, H. L.; Brown, T. L. J. Am. Chem. Soc. 1970, 92, 4664.
81. (g) Hsieh, H. L.; Quirk, R. P. Anionic Polymerization: Principles and Practical Applications; Marcel Dekker: New York, 1996.
82. Arene-lithium interactions have been discussed extensively by Dougherty and coworkers. Ma, J. C.; Dougherty, D. A. Chem. Rev. 1997, 97, 1303.
83. For spectroscopic studies of LDA mixed aggregates in HMPA/THF mixtures, see refs 4c and 6b. For analogous computational studies, see ref 7e.
84. Singh, K.; Collum, D. B. J. Am. Chem. Soc. 2006, 128, 13753.
85. The concentration of LDA, although expressed as molarity, refers to the concentration of the monomer unit (normality). The concentrations of ethereal solvent and HMPA are expressed as total concentration of free (uncoordinated) ligand.
86. Rein, A. J.; Donahue, S. M.; Pavlosky, M. A. Curr. Opin. Drug Discovery Dev. 2000, 3, 734.
87. Espenson, J. H. Chemical Kinetics and Reaction Mechanisms; McGrawHill: New York, 1995; p 15.
88. Jackman, L.-M.; Scarmoutzos, L.-M.; Porter, W. J. Am. Chem. Soc. 1987, 109, 6524;
89. Jackman, L.-M.; Scarmoutzos, L.-M.; Smith, B. D.; Williard, P. G. J. Am. Chem. Soc. 1988, 110, 6058;
90. Zuend, S. J.; Ramirez, A.; Lobkovsky, E.; Collum, D. B. J. Am. Chem. Soc. 2006, 128, 5939.
91. We define the idealized rate law as that obtained by rounding the observed reaction orders to the nearest rational order.
92. (a) Remenar, J. F.; Lucht, B. L.; Collum, D. B. J. Am. Chem. Soc. 1997, 119, 5567.
93. (b) Lucht, B. L.; Collum, D. B. J. Am. Chem. Soc. 1995, 117, 9863.
94. 2O (1). The lack of correlation with measured binding constants (ref 32) further argues against a primary-shell effect.
95. Reactions of LDA with a number of substrates in THF at -78°C display linear plots of substrate concentration versus time as well as odd sigmoidal behaviors, all of which are part of an ongoing study.
96. 2 moiety form hexamers in solution: McNeil, A. J.; Toombes, G. E. S.; Gruner, S. M.; Lobkovsky, E.; Collum, D. B.; Chandramouli, S. V.; Vanasse, B. J.; Ayers, T. A. J. Am. Chem. Soc. 2004, 126, 16559.
97. Leading references to mixed solvation: Qu, B.; Collum, D. B. J. Am. Chem. Soc. 2005, 127, 10820.
98. (a) Stanetty, P.; Mihovilovic, M. D. J. Org. Chem. 1997, 62, 1514.
99. (b) Aubrecht, K. B.; Collum, D. B. J. Org. Chem. 1996, 61, 8674.
100. (c) Bernstein, M.P.; Romesberg, F. E.; Fuller, D. J.; Harrison, A. T.; Williard, P. G.; Liu, Q. Y.; Collum, D. B. J. Am. Chem. Soc. 1992, 114, 5100 and references cited therein.
101. Morgan and coworkers investigated the elimination of cyclopentene oxide by LDA/HMPA, apparently in the absence of base-labile ethereal ligands (ref 16a,b).
102. For additional leading references to spectroscopic, crystallographic, and kinetic evidence of open dimers, see: Zhao, P.; Collum, D. B. J. Am. Chem. Soc. 2003, 125, 14411.
103. Bell, R. P. The Tunnel Effect in Chemistry; Chapman & Hall: New York, 1980.
104. For leading references to oxacarbenoids, see: Pratt, Lawrence, M.; Ramachandran, B. J. Org. Chem. 2005, 70, 7238;
105. Boche, G.; Lohrenz, J. C. W. Chem. Rev. 2001, 101, 697.
106. Seebach, D.; Aebi, J.-D. Helv. Chim. Acta 1985, 68, 1507.
107. Singh, K.; Collum, D. B. J. Am. Chem. Soc. 2006, 128, 13753.
108. For discussions of steric effects on lithium ion solvation by HMPA, see: (a) Ishiguro, S. Pure Appl. Chem. 1994, 66, 393.
109. (b) Dack, M. R. J.; Bird, K. J.; Parker, A. J. Aust. J. Chem. 1975, 28, 955.
110. (c) Ishiguro, S. Bull. Chem. Soc. Jpn. 1997, 70, 1465.
111. Burford, N.; Royan, B. W.; Spence, R. E. v. H.; T. Cameron, S.; Linden, A.; Rogers, R. D. J. Chem. Soc., Dalton Trans. 1990, 1521.
112. HMPA has been estimated to bind 300 times more strongly than THF in one case (ref 2a).