Regioselective, Diastereoselective, and Enantioselective Lithiation-Substitution Sequences: Reaction Pathways and Synthetic Applications

Accounts of Chemical Research

Volumn 29, Issue 11, 1996, Pages 552-560

  Beak, Peter ^a,b,c   Basu, Amit ^a,d,e   Gallagher, Donald J ^a,f,g   Park, Yong Sun ^a,h   Thayumanavan, S ^a,i,j  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

^b HARVARD UNIVERSITY   (United States)

^c IOWA STATE UNIVERSITY   (United States)

^d REED COLLEGE   (United States)

^e PRINCETON UNIVERSITY   (United States)

^f TUFTS UNIVERSITY   (United States)

^g PFIZER INC   (United States)

^h Yonsei University   (South Korea)

ⁱ American College   (India)

^j CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

more..

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000679903     PISSN: 00014842     EISSN: None     Source Type: Journal    
DOI: 10.1021/ar950142b     Document Type: Article

References (62)

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2. Boche, G. Angew. Chem., Int. Ed. Engl. 1989, 28, 277-297. Collum, D. B. Acc. Chem. Res. 1993, 26, 227-234. Setzer, W. N.; Schleyer, P. v. R. Adv. Organomet. Chem. 1985, 24, 354-451. Schlosser, M. Ed. Tetrahedron 1994, 50, 5845-6128.
3. Boche, G. Angew. Chem., Int. Ed. Engl. 1989, 28, 277-297. Collum, D. B. Acc. Chem. Res. 1993, 26, 227-234. Setzer, W. N.; Schleyer, P. v. R. Adv. Organomet. Chem. 1985, 24, 354-451. Schlosser, M. Ed. Tetrahedron 1994, 50, 5845-6128.
4. Boche, G. Angew. Chem., Int. Ed. Engl. 1989, 28, 277-297. Collum, D. B. Acc. Chem. Res. 1993, 26, 227-234. Setzer, W. N.; Schleyer, P. v. R. Adv. Organomet. Chem. 1985, 24, 354-451. Schlosser, M. Ed. Tetrahedron 1994, 50, 5845-6128.
5. Gray, M.; Tinkl, M.; Snieckus, V. In Comprehensive Organometallic Chemistry; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds,; Elsevier Science Ltd.: New York, 1995; Vol. 11, Chapter 1 and references cited therein.
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8. Hoppe, D.; Hintze, F.; Tebben, P.; Paetow, M.; Aherns, H.; Schwerdtfeger, J.; Sommerfeld, P.; Haller, J.; Guarnieri, W.; Kolczewski, S.; Hense, T.; Hoppe, I. Pure Appl. Chem. 1994, 66, 1479-1486. Tomioka, K. Synthesis 1990, 541-549. Cox, P. J.; Simpkins, N. S. Tetrahedron: Asymmetry 1991, 2, 1-26. Koga, K.; Shindo, M. J. Synth. Org. Chem. Jpn. 1995, 53, 1021-1032.
9. Hoppe, D.; Hintze, F.; Tebben, P.; Paetow, M.; Aherns, H.; Schwerdtfeger, J.; Sommerfeld, P.; Haller, J.; Guarnieri, W.; Kolczewski, S.; Hense, T.; Hoppe, I. Pure Appl. Chem. 1994, 66, 1479-1486. Tomioka, K. Synthesis 1990, 541-549. Cox, P. J.; Simpkins, N. S. Tetrahedron: Asymmetry 1991, 2, 1-26. Koga, K.; Shindo, M. J. Synth. Org. Chem. Jpn. 1995, 53, 1021-1032.
10. Klute, W.; Dress, R.; Hoffmann, R. W. J. Chem. Soc., Perkin Trans. 2 1993, 1409-1411. Hoffmann, R. W.; Julius, M.; Chemla, F.; Ruhland, T.; Frenzen, G. Tetrahedron 1994, 50, 6049-6060. Hoffmann, R. W.; Dress, R. K.; Ruhland, T.; Wenzel, A. Chem. Ber. 1995, 128, 861-870.
11. Klute, W.; Dress, R.; Hoffmann, R. W. J. Chem. Soc., Perkin Trans. 2 1993, 1409-1411. Hoffmann, R. W.; Julius, M.; Chemla, F.; Ruhland, T.; Frenzen, G. Tetrahedron 1994, 50, 6049-6060. Hoffmann, R. W.; Dress, R. K.; Ruhland, T.; Wenzel, A. Chem. Ber. 1995, 128, 861-870.
12. Klute, W.; Dress, R.; Hoffmann, R. W. J. Chem. Soc., Perkin Trans. 2 1993, 1409-1411. Hoffmann, R. W.; Julius, M.; Chemla, F.; Ruhland, T.; Frenzen, G. Tetrahedron 1994, 50, 6049-6060. Hoffmann, R. W.; Dress, R. K.; Ruhland, T.; Wenzel, A. Chem. Ber. 1995, 128, 861-870.
13. Elworthy, T. R.; Meyers, A. I. Tetrahedron 1994, 50, 6089-6096. Gawley, R. E.; Zhang, Q. Tetrahedron 1994, 50, 6077-6088.
14. Elworthy, T. R.; Meyers, A. I. Tetrahedron 1994, 50, 6089-6096. Gawley, R. E.; Zhang, Q. Tetrahedron 1994, 50, 6077-6088.
15. Brown, T. L. Pure Appl. Chem. 1970, 23, 447-462. Polyamine-Chelated Alkali metal Compounds; Langer, A. W., Jr., Ed.; American Chemical Society: Washington, DC, 1974.
16. Brown, T. L. Pure Appl. Chem. 1970, 23, 447-462. Polyamine-Chelated Alkali metal Compounds; Langer, A. W., Jr., Ed.; American Chemical Society: Washington, DC, 1974.
17. Beak, P.; Meyers, A. I. Acc. Chem. Res. 1986, 19, 356-363. Klumpp, G. Reel. Trav. Chim. Pays.-Bas 1986, 105, 1-21 and references cited therein.
18. Beak, P.; Meyers, A. I. Acc. Chem. Res. 1986, 19, 356-363. Klumpp, G. Reel. Trav. Chim. Pays.-Bas 1986, 105, 1-21 and references cited therein.
19. Hay, D. R.; Song, Z.; Smith, S. G.; Beak, P. J. Am. Chem. Soc. 1988, 110, 8145-8153. Gallagher, D. J.; Kerrick, S. T.; Beak, P. J. Am. Chem. Soc. 1992, 114, 5872-5873. Resek, J.; Beak, P. J. Am. Chem. Soc 1994, 116, 405-406. Gallagher, D. J.; Beak, P. J. Org. Chem. 1995, 60, 7092-7093.
20. Hay, D. R.; Song, Z.; Smith, S. G.; Beak, P. J. Am. Chem. Soc. 1988, 110, 8145-8153. Gallagher, D. J.; Kerrick, S. T.; Beak, P. J. Am. Chem. Soc. 1992, 114, 5872-5873. Resek, J.; Beak, P. J. Am. Chem. Soc 1994, 116, 405-406. Gallagher, D. J.; Beak, P. J. Org. Chem. 1995, 60, 7092-7093.
21. Hay, D. R.; Song, Z.; Smith, S. G.; Beak, P. J. Am. Chem. Soc. 1988, 110, 8145-8153. Gallagher, D. J.; Kerrick, S. T.; Beak, P. J. Am. Chem. Soc. 1992, 114, 5872-5873. Resek, J.; Beak, P. J. Am. Chem. Soc 1994, 116, 405-406. Gallagher, D. J.; Beak, P. J. Org. Chem. 1995, 60, 7092-7093.
22. Hay, D. R.; Song, Z.; Smith, S. G.; Beak, P. J. Am. Chem. Soc. 1988, 110, 8145-8153. Gallagher, D. J.; Kerrick, S. T.; Beak, P. J. Am. Chem. Soc. 1992, 114, 5872-5873. Resek, J.; Beak, P. J. Am. Chem. Soc 1994, 116, 405-406. Gallagher, D. J.; Beak, P. J. Org. Chem. 1995, 60, 7092-7093.
23. For early work on amide-directed lithiations of piperidines see: Beak, P.; Zajdel, W. J. J. Am. Chem. Soc. 1984, 106, 1010-1018. For introduction of the Boc group as a directing and stabilizing group see: Beak, P.; Lee, W-K. Tetrahedron Lett. 1989, 30, 1197-1200. For the Bocpiperidines see: Beak, P.; Lee, W-K. J. Org. Chem. 1990, 55, 2578-2580. Beak, P.; Lee, W-K. J. Org. Chem. 1993, 58, 1109-1117.
24. For early work on amide-directed lithiations of piperidines see: Beak, P.; Zajdel, W. J. J. Am. Chem. Soc. 1984, 106, 1010-1018. For introduction of the Boc group as a directing and stabilizing group see: Beak, P.; Lee, W-K. Tetrahedron Lett. 1989, 30, 1197-1200. For the Bocpiperidines see: Beak, P.; Lee, W-K. J. Org. Chem. 1990, 55, 2578-2580. Beak, P.; Lee, W-K. J. Org. Chem. 1993, 58, 1109-1117.
25. For early work on amide-directed lithiations of piperidines see: Beak, P.; Zajdel, W. J. J. Am. Chem. Soc. 1984, 106, 1010-1018. For introduction of the Boc group as a directing and stabilizing group see: Beak, P.; Lee, W-K. Tetrahedron Lett. 1989, 30, 1197-1200. For the Bocpiperidines see: Beak, P.; Lee, W-K. J. Org. Chem. 1990, 55, 2578-2580. Beak, P.; Lee, W-K. J. Org. Chem. 1993, 58, 1109-1117.
26. For early work on amide-directed lithiations of piperidines see: Beak, P.; Zajdel, W. J. J. Am. Chem. Soc. 1984, 106, 1010-1018. For introduction of the Boc group as a directing and stabilizing group see: Beak, P.; Lee, W-K. Tetrahedron Lett. 1989, 30, 1197-1200. For the Bocpiperidines see: Beak, P.; Lee, W-K. J. Org. Chem. 1990, 55, 2578-2580. Beak, P.; Lee, W-K. J. Org. Chem. 1993, 58, 1109-1117.
27. Houk, K. N.; Rondan, N. G.; Beak, P.; Zajdel, W. J.; Schleyer, P. v. R.; Chandrashekhar, J. J. Org. Chem. 1981, 46, 4108-4110. Bach, R. D.; Braden, M. L.; Wolber, G. J. J. Org. Chem. 1983, 48, 1509-1514.
28. Houk, K. N.; Rondan, N. G.; Beak, P.; Zajdel, W. J.; Schleyer, P. v. R.; Chandrashekhar, J. J. Org. Chem. 1981, 46, 4108-4110. Bach, R. D.; Braden, M. L.; Wolber, G. J. J. Org. Chem. 1983, 48, 1509-1514.
29. Lutz, G. P.; Wallin, A. P.; Kerrick, S. T.; Beak, P. J. Org. Chem. 1991, 56, 4938-4943.
30. Nozaki, H.; Aratani, T.; Toraya, T.; Noyori, R. Tetrahedron 1971, 27, 905-913.
31. Hoppe, D.; Hintze, F.; Tebben, P. Angew. Chem., Int. Ed. Engl. 1990, 29, 1422-1424.
32. Kerrick, S. T.; Beak, P. J. Am. Chem. Soc. 1991, 113, 9708-9710.
33. Efforts to identify other chiral ligands for the asymmetric deprotonation of N-Boc-pyrrolidine have been reported. Gallagher, D. J.; Wu, S.; Nikolic, N. A.; Beak, P. J. Org. Chem. 1995, 60, 8148.
34. The organolithium (R)-17 was reported to be configurationally labile in the absence of diamine in our preliminary communication (ref 14). This was found to be in error and corrected in the full paper (ref 17).
35. Beak, P.; Kerrick, S. T.; Wu, S.; Chu, J. J. Am. Chem. Soc. 1994, 116, 3231-3239.
36. Rauenstrach, V.; Mégard, P.; Bourdin, B.; Furrer, A. J. Am. Chem. Soc. 1992, 114, 1418-1428. The major reaction of the minor enantiomer and the minor reaction of the major enantiomer provide the meso diastereomer (R,S)-24 in low yield.
37. Wu, S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1996, 118, 715-721.
38. High H-D isotope effects have been observed for these reactions. Hoppe, D.; Paetow, M.; Hintze. Angew Chem., Int. Ed. Engl. 1993, 32, 394-396. Kaiser, B.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 323-325. See also ref 11.
39. High H-D isotope effects have been observed for these reactions. Hoppe, D.; Paetow, M.; Hintze. Angew Chem., Int. Ed. Engl. 1993, 32, 394-396. Kaiser, B.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 323-325. See also ref 11.
40. Park, Y. S.; Boys, M. L,; Beak, P. J. Am. Chem. Soc. 1996, 118, 3757-3758.
41. The configuration of the organostannane 32 was assigned as S in the original communication (ref 21), under the assumption that the organolithium underwent an invertive substitution with all electrophiles. Greater consistency with other results is achieved by assuming retentive substitution and invertive stannylation. However, these assignments remain provisional.
42. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2516-2518.
43. Noyori, R.; Tokunaga, M.; Kitamura, M. Bull. Chem. Soc. Jpn. 1995, 68, 36-56 and references cited therein. In this paper, Noyori et al. define a dynamic kinetic resolution as a process in which enantiomers can interconvert under the reaction conditions and provide an elegant kinetic analysis. The definition can be extended to include situations that involve interconverting diastereomers. In that case, the kinetic analysis outlined by Seeman must be used. Seeman, J. I. Chem. Rev. 1983, 83, 83-134. For a recent application see: Gately, D. A.; Norton, J. A. J. Am. Chem. Soc. 1996, 118, 3479-3489. For a related discussion, see: Hirsch, R.; Hoffmann, R. W. Chem. Ber. 1992,126, 975-982.
44. Noyori, R.; Tokunaga, M.; Kitamura, M. Bull. Chem. Soc. Jpn. 1995, 68, 36-56 and references cited therein. In this paper, Noyori et al. define a dynamic kinetic resolution as a process in which enantiomers can interconvert under the reaction conditions and provide an elegant kinetic analysis. The definition can be extended to include situations that involve interconverting diastereomers. In that case, the kinetic analysis outlined by Seeman must be used. Seeman, J. I. Chem. Rev. 1983, 83, 83-134. For a recent application see: Gately, D. A.; Norton, J. A. J. Am. Chem. Soc. 1996, 118, 3479-3489. For a related discussion, see: Hirsch, R.; Hoffmann, R. W. Chem. Ber. 1992,126, 975-982.
45. Noyori, R.; Tokunaga, M.; Kitamura, M. Bull. Chem. Soc. Jpn. 1995, 68, 36-56 and references cited therein. In this paper, Noyori et al. define a dynamic kinetic resolution as a process in which enantiomers can interconvert under the reaction conditions and provide an elegant kinetic analysis. The definition can be extended to include situations that involve interconverting diastereomers. In that case, the kinetic analysis outlined by Seeman must be used. Seeman, J. I. Chem. Rev. 1983, 83, 83-134. For a recent application see: Gately, D. A.; Norton, J. A. J. Am. Chem. Soc. 1996, 118, 3479-3489. For a related discussion, see: Hirsch, R.; Hoffmann, R. W. Chem. Ber. 1992,126, 975-982.
46. Noyori, R.; Tokunaga, M.; Kitamura, M. Bull. Chem. Soc. Jpn. 1995, 68, 36-56 and references cited therein. In this paper, Noyori et al. define a dynamic kinetic resolution as a process in which enantiomers can interconvert under the reaction conditions and provide an elegant kinetic analysis. The definition can be extended to include situations that involve interconverting diastereomers. In that case, the kinetic analysis outlined by Seeman must be used. Seeman, J. I. Chem. Rev. 1983, 83, 83-134. For a recent application see: Gately, D. A.; Norton, J. A. J. Am. Chem. Soc. 1996, 118, 3479-3489. For a related discussion, see: Hirsch, R.; Hoffmann, R. W. Chem. Ber. 1992,126, 975-982.
47. Figure 2 depicts epimerization of the diastereomeric complexes proceeding directly without the intermediacy of the uncomplexed organolithium. In a recent study of α-selenoorganolithium reagents, Hoffmann has shown that epimerization occurs faster than decomplexation followed by epimerization. However, we cannot rule out a pathway involving decomplexation followed by inversion. Hoffmann, R. W.; Klute, W.; Dress, R. K.; Wenzel, A. J. Chem. Soc., Perkin Trans. 2 1995, 1721-1726.
48. Basu, A.; Beak, P. J. Am. Chem. Soc. 1996, 118, 1575-1576.
49. Basu, A.; Gallagher, D. J.; Beak, P. J. Org. Chem. 1996, 61, 5718-5719.
50. Gallagher, D. J.; Du, H.; Long, S. A.; Beak, P. J. Am. Chem. Soc., in press.
51. Marsch, M.; Harms, K.; Zschage, O.; Hoppe, D.; Boche, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 321-323.
52. Thayumanavan, S.; Lee, S.; Liu, C.; Beak, P. J. Am. Chem. Soc. 1994, 116, 9755-9756.
53. Schlosser, M.; Limat, D. J. Am. Chem. Soc. 1995, 117, 12342-12343.
54. Hoppe and Boche have determined the solid state structures of an α-lithio oxygen dipole-stabilized carbanion and a lithiated 1-butyl-indene which are complexed to (-)-sparteine. See ref 29 and Hoppe, I.; Marsch, M.; Harms, K.; Boche, G.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 2158-2160. The stereochemistry of the products from the reactions of these carbanions with electrophiles does not show a highly consistent pattern. Hoppe and Gawley have reported reactions in which a single substrate undergoes substitution with similar electrophiles with both retention and inversion. Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097-6108. Gawley, R. E.; Zhang, Q. J. Org. Chem. 1995, 60, 5763-5769. Our assignments of absolute configuration are consistent with the stereochemical course of the majority of known reactions, but, as noted, they are not definitive.
55. Hoppe and Boche have determined the solid state structures of an α-lithio oxygen dipole-stabilized carbanion and a lithiated 1-butyl-indene which are complexed to (-)-sparteine. See ref 29 and Hoppe, I.; Marsch, M.; Harms, K.; Boche, G.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 2158-2160. The stereochemistry of the products from the reactions of these carbanions with electrophiles does not show a highly consistent pattern. Hoppe and Gawley have reported reactions in which a single substrate undergoes substitution with similar electrophiles with both retention and inversion. Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097-6108. Gawley, R. E.; Zhang, Q. J. Org. Chem. 1995, 60, 5763-5769. Our assignments of absolute configuration are consistent with the stereochemical course of the majority of known reactions, but, as noted, they are not definitive.
56. Hoppe and Boche have determined the solid state structures of an α-lithio oxygen dipole-stabilized carbanion and a lithiated 1-butyl-indene which are complexed to (-)-sparteine. See ref 29 and Hoppe, I.; Marsch, M.; Harms, K.; Boche, G.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 2158-2160. The stereochemistry of the products from the reactions of these carbanions with electrophiles does not show a highly consistent pattern. Hoppe and Gawley have reported reactions in which a single substrate undergoes substitution with similar electrophiles with both retention and inversion. Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097-6108. Gawley, R. E.; Zhang, Q. J. Org. Chem. 1995, 60, 5763-5769. Our assignments of absolute configuration are consistent with the stereochemical course of the majority of known reactions, but, as noted, they are not definitive.
57. Lutz, G. P.; Du, H.; Gallagher, D. J.; Beak, P. J. Org. Chem. 1996, 61, 4542-4554.
58. Muci, A. R.; Campos, K. R.; Evans, D. A. J. Am. Chem. Soc. 1995, 117, 9075-9076.
59. Tsukazaki, M.; Tinkl, M.; Roglans, A.; Chapell, B. J., Taylor, N. J.; Snieckus, V. J. Am. Chem. Soc. 1996, 118, 685-686.
60. Hodgson, D. M.; Lee, G. P. J. Chem. Soc. Chem. Commun. 1996, 1015-1016.
61. Thayumanavan, S.; Beak, P.; Curran, D. P. Tetrahedron Lett. 1996, 37, 2899-2902.
62. In this regard the recent study by Hoffmann and co-workers demonstrating the ability to control the rate of reaction of diastereomeric complexes with electrophiles relative to the rates of reaction with uncomplexed organolithiums represents a significant advance toward catalysis. Hoffmann, R. W.; Klute, W. Chem. Eur. J. 1996, 2, 694-700.