Pseudoephedrine as a practical chiral auxiliary for the synthesis of highly enantiomerically enriched carboxylic acids, alcohols, aldehydes, and ketones

Journal of the American Chemical Society

Volumn 119, Issue 28, 1997, Pages 6496-6511

  Myers, Andrew G ^a   Yang, Bryant H ^a   Chen, Hou ^a   McKinstry, Lydia ^a   Kopecky, David J ^a   Gleason, James L ^a  

^a California Institute of Technology ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; ALKANOL; AMIDE; CARBOXYLIC ACID DERIVATIVE; KETONE; PSEUDOEPHEDRINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; ENANTIOMER; IN VITRO STUDY; INFRARED SPECTROPHOTOMETRY; MASS SPECTROMETRY; METHODOLOGY; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030810476     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja970402f     Document Type: Article

References (79)

1. (a) Evans, D. A. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1984; Vol. 3, pp 1-110.
2. (b) Lutomski, K. A.; Meyers, A. I. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1984; Vol. 3, pp 213-274.
3. (c) Seebach, D.; Imwinkelried, R.; Weber, T. In Modern Synthetic Synthesis; Scheffold, R., Ed.; Springer: Berlin-Heidelberg, 1986; Vol. 4, pp 125-259.
4. (d) Crosby, J. Tetrahedron 1991, 47, 4789.
5. (e) Caine, D. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 3, pp 1-63.
6. Meyers, A. I.; Knaus, G.; Kamata, K.; Ford, M. E. J. Am. Chem. Soc. 1976, 98, 567.
7. (a) Evans, D. A.; Takacs, J. M. Tetrahedron Lett. 1980, 21, 4233.
8. (b) Sonnet, P.; Heath, R. R. J. Org. Chem. 1980, 45, 3137.
9. Kawanami, Y.; Ito, Y.; Kitagawa, T.; Taniguchi, Y.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett. 1984, 25, 857.
10. For additional examples, see: (a) Davies, S. G. Pure Appl. Chem. 1988, 60, 13. (b) Drewes, S. E.; Malissar, D. G. S.; Roos, G. H. O. Chem. Ber. 1993, 126, 2663. (c) Abiko, A.; Moriya, O.; Filla, S. A.; Masamune, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 793.
11. For additional examples, see: (a) Davies, S. G. Pure Appl. Chem. 1988, 60, 13. (b) Drewes, S. E.; Malissar, D. G. S.; Roos, G. H. O. Chem. Ber. 1993, 126, 2663. (c) Abiko, A.; Moriya, O.; Filla, S. A.; Masamune, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 793.
12. For additional examples, see: (a) Davies, S. G. Pure Appl. Chem. 1988, 60, 13. (b) Drewes, S. E.; Malissar, D. G. S.; Roos, G. H. O. Chem. Ber. 1993, 126, 2663. (c) Abiko, A.; Moriya, O.; Filla, S. A.; Masamune, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 793.
13. (a) Evans, D. A.; Ennis, M. D.; Mathre, D. J. J. Am. Chem. Soc. 1982, 104, 1737.
14. (b) Mathre, D. Ph.D. Thesis, California Institute of Technology, 1985.
15. (a) Oppolzer, W.; Moretti, R.; Thomi, S. Tetrahedron Lett. 1989, 30, 5603.
16. (b) For a previous camphor-derived system, see: Schmierer, R.; Grotemeier, G.; Helmchen, G.; Selim, A. Angew. Chem., Int. Ed. Engl. 1981, 20, 207.
17. Myers, A. G.; Yang, B. H.; Chen, H.; Gleason, J. L. J. Am. Chem. Soc. 1994, 116, 9361.
18. For the specific case of the alkylation of pseudoephedrine glycinamide and its application to the preparation of highly enantiomerically enriched α-amino acids, see: (a) Myers, A. G.; Gleason, J. L.; Yoon, T.; Kung, D. W. J. Am. Chem. Soc. 1997, 119, 656. (b) Myers, A. G.; Gleason, J. L.; Yoon, T. J. Am. Chem. Soc. 1995, 117, 8488.
19. For the specific case of the alkylation of pseudoephedrine glycinamide and its application to the preparation of highly enantiomerically enriched α-amino acids, see: (a) Myers, A. G.; Gleason, J. L.; Yoon, T.; Kung, D. W. J. Am. Chem. Soc. 1997, 119, 656. (b) Myers, A. G.; Gleason, J. L.; Yoon, T. J. Am. Chem. Soc. 1995, 117, 8488.
20. For the use of the acyclic amino alcohol phenylglycinol as a chiral auxiliary, see: (a) Micouin, L.; Schanen, V.; Riche, C.; Chiaroni, A.; Quirion, J-C.; Husson, H-P. Tetrahedron Lett. 1994, 35, 7223. (b) Micouin, L.; Jullian, V.; Quirion, J-C.; Husson, H-P. Tetrahedron: Asymmetry 1996, 7, 2839.
21. For the use of the acyclic amino alcohol phenylglycinol as a chiral auxiliary, see: (a) Micouin, L.; Schanen, V.; Riche, C.; Chiaroni, A.; Quirion, J-C.; Husson, H-P. Tetrahedron Lett. 1994, 35, 7223. (b) Micouin, L.; Jullian, V.; Quirion, J-C.; Husson, H-P. Tetrahedron: Asymmetry 1996, 7, 2839.
22. (a) Schmidt, E.; Calliess, F. W. Arch. Pharm. 1912, 250, 154.
23. (b) Mitchell, W. J. Chem. Soc. 1940, 1153.
24. (c) Welsh, L. H. J. Am. Chem. Soc. 1947, 69, 128.
25. Myers, A. G.; Yang, B. H. Submitted for publication in Org. Synth.
26. Myers, A. G.; Yoon, T.; Gleason, J. L. Tetrahedron Lett. 1995, 36, 4555.
27. This stands in contrast to the alkylation of the enolate derived from pseudoephedrine glycinamide (ref 9), where the selectivity of the alkylation with ethyl iodide was diminished in the absence of lithium chloride (97% de with lithium chloride versus 82% de without lithium chloride).
28. (a) Seebach, D.; Bossler, H.; Gründler, H.; Shoda, S.-I. Helv. Chim. Acta 1991, 74, 197.
29. (b) Miller, S. A.; Griffiths, S. L.; Seebach, D. Helv. Chim. Acta 1993, 76, 563.
30. (c) Bossler, H. G.; Seebach, D. Helv. Chim. Acta 1994, 77, 1124.
31. (a) Imide enolates, by contrast, are essentially inert toward these same substrates (ref 6b).
32. (b) The presence of lithium chloride in the reaction medium did not alter this outcome. Thus, the lithium enolate derived from the imide N-propionylbenzyloxazolidinone was found not to react with n-butyl iodide at 0 °C in the presence of 10 equiv of lithium chloride after 16 h (Myers, A. G.; Chen, H., California Institute of Technology, unpublished results).
33. Fewer equivalents of the enolate can be employed. For example, alkylation of 1.3 equiv of the enolate derived from 1 with the iodide 78 at 23 °C for 20.5 h afforded the 1,3-syn alkylation product 35 in 90% yield with 99:1 selectivity (cf. entry 4, Table 3).
34. Myers, A. G.; Yang, B. H.; Chen, H.; Kopecky, D. J. Synlett 1997, 5, 457.
35. The iodide 78 was prepared by iodination of the corresponding alcohol, prepared in ≥99% de and 90% yield by LAB reduction (see text) of the alkylation product 12. For iodination of alcohols, see: (a) Garegg, P. J.; Samuelsson, B. J. Chem. Soc., Perkin Trans. 1 1980, 2866. (b) Lange, G. L.; Gottardo, C. Synth. Commun. 1990, 20, 1473.
36. The iodide 78 was prepared by iodination of the corresponding alcohol, prepared in ≥99% de and 90% yield by LAB reduction (see text) of the alkylation product 12. For iodination of alcohols, see: (a) Garegg, P. J.; Samuelsson, B. J. Chem. Soc., Perkin Trans. 1 1980, 2866. (b) Lange, G. L.; Gottardo, C. Synth. Commun. 1990, 20, 1473.
37. In these and all subsequent alkylation reactions, care was taken to avoid adventitious diastereomeric enrichment upon purification and de values reported reflect those of the crude reaction mixtures.
38. 6 as solvent: (a) Hatton, J. V.; Richards, R. E. Mol. Phys. 1960, 3, 253.
39. (b) Hatton, J. V.; Richards, R. E. Mol. Phys. 1962, 5, 139.
40. (c) Stewart, W. E.; Siddall, T. H., III. Chem. Rev. 1970, 5, 517.
41. Myers, A. G.; McKinstry, L. J. Org. Chem. 1996, 61, 2428.
42. Myers, A. G.; McKinstry, L.; Barbay, J. K. Manuscript in preparation.
43. Myers, A. G.; Yang, B. H.; Chen, H. Submitted for publication in Org. Synth.
44. (a) Uffer, H.; Schlittler, E. Helv. Chim. Acta 1948, 31, 1397.
45. (b) Gaylord, N. G. Reductions with Complex Metal Hydrides; Wiley-Interscience: New York, 1956; pp 544-592.
46. (c) Zabicky, J., Ed. The Chemistry of Amides; Wiley-Interscience: New York, 1970; pp 795-801.
47. (a) Brown, H. C.; Heim, P. J. Am. Chem. Soc. 1964, 86, 3566.
48. (b) Brown, H. C.; Narasimhan, S.; Choi, Y. M. Synthesis 1981, 441.
49. (c) Brown, H. C.; Narasimhan, S.; Choi, Y. M. Synthesis 1981, 996.
50. Brown, H. C.; Kim, S. C. Synthesis 1977, 635.
51. Brown, H. C.; Krishnamurthy, S.; Yoon, N. M. J. Org. Chem. 1976, 41, 1778.
52. Hutchins, R. O.; Learn, K.; El-Telbany, F.; Stercho, Y. P. J. Org. Chem. 1984, 49, 2438.
53. (a) Fisher, G. B.; Harrison, J.; Fuller, J. C.; Goralski, C. T.; Singaram, B. Tetrahedron Lett. 1992, 33, 4533.
54. (b) Fisher, G. B.; Fuller, J. C.; Harrison, J.; Goralski, C. T.; Singaram, B. Tetrahedron Lett. 1993, 34, 1091.
55. (c) Fisher, G. B.; Fuller, J. C.; Harrison, J.; Alvarez, S. G.; Burkhardt, E. R.; Goralski, C. T.; Singaram, B. J. Org. Chem. 1994, 59, 6378.
56. Myers, A. G.; Yang, B. H.; Kopecky, D. J. Tetrahedron Lett. 1996, 37, 3623.
57. (a) Andrews, G. C.; Crawford, T. C. Tetrahedron Lett. 1980, 21, 693.
58. (b) Andrews, G. C.; Crawford, T. C. Tetrahedron Lett. 1980, 21, 697.
59. Brown, H. C.; Tsukamoto, A. J. Am. Chem. Soc. 1964, 86, 1089.
60. In all cases, the pseudoephedrine aminal was found to be a single diastereomer, of undetermined stereochemistry.
61. (a) Evans, E. A. J. Chem. Soc. 1956, 4691.
62. (b) Evans, E. A. Chem. Ind. (London) 1957, 1596.
63. (c) Izzo, P. T.; Safir, S. R. J. Org. Chem. 1959, 24, 701.
64. Askin, D.; Volante, R. P.; Ryan, K. M.; Reamer, R. A.; Shinkai, I. Tetrahedron Lett. 1988, 29, 4245.
65. Hoffman, R. W. Chem. Rev. 1989, 89, 1841.
66. (a) Larcheveque, M.; Ignatova, E.; Cuvigny, T. Tetrahedron Lett. 1978, 3961.
67. (b) Larcheveque, M.; Ignatova, E.; Cuvigny, T. J. Organomet. Chem. 1979, 177, 5.
68. For example, enolization of ephedrine propionamide (1 equiv) with LDA (2.1 equiv) in the presence of lithium chloride (6 equiv), as described for pseudoephedrine propionamide, and addition of n-butyl iodide at 0 °C afforded a diastereomeric mixture of alkylation products (70% de, configuration not determined) in 90% yield after purification by flash column chromatography.
69. Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923.
70. Kofron, W. G.; Baclawski, L. M. J. Org. Chem. 1976, 41, 1879.
71. Connor, D. S.; Klein, G. W.; Taylor, G. N.; Boeckman, R. K., Jr.; Medwid, J. B. Organic Syntheses; Collect. Vol. VI, Wiley: New York, 1988; p 101.
72. Ohwa, M.; Eliel, E. L. Chem. Lett. 1987, 41.
73. Dale, J. A.; Dull, D. L.; Mosher, H. S. J. Org. Chem. 1969, 34, 2543.
74. Watson, M. B.; Youngson, G. W. J. Chem. Soc. C 1968, 258.
75. In each case, an authentic sample of the minor diastereomeric alkylation product was prepared for comparative analysis (chiral capillary GC analysis of the corresponding trimethylsilyl ether or acetate ester). In the case of amides 16, 21, 26, 27, and 29-31, diastereomeric mixtures of α-epimers were obtained by epimerization with LDA (5 equiv) or lithium 2,2,6,6-tetramethylpiperidide (5 equiv) in THF for 5 h at 23 °C followed by quenching with aqueous ammonium chloride solution. Amide 28 was epimerized by stirring with lithium chloride (5 equiv) in N,N-dimethylformamide at 23 °C for 12 h. Each of the remaining alkylation products in Tables 2 and 3 was epimerized by stirring the substrate with trifluoroacetic acid (10 equiv) in THF at reflux for 1 h (effecting N → O acyl transfer as well as α-epimerization), followed by neutralization with aqueous sodium bicarbonate solution at 23 °C for 24 h (causing O → N acyl transfer).
76. In each case, an authentic sample of the minor diastereomeric (R)-α-methylbenzyl amide was prepared for comparative analysis.
77. Acetate esters of the diastereomeric alcohol pairs 68 and 69, 70 and 71, 72 and 73, 74 and 75, and 76 and 77 were separated with baseline resolution when assayed by chiral capillary GC analysis.
78. Kraus, G. A.; Taschner, J. J. Org. Chem. 1980, 45, 1175 and references therein.
79. Both (R)-and (S)-Mosher ester derivatives were prepared for comparative analysis.