Catalytic enantioselective conjugate reduction of lactones and lactams

Journal of the American Chemical Society

Volumn 125, Issue 37, 2003, Pages 11253-11258

  Hughes, Gregory ^a   Kimura, Masanari ^a   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

LACTONES;

ADDITION REACTIONS; ALCOHOLS; CATALYSIS; ESTERS; SYNTHESIS (CHEMICAL);

ORGANIC POLYMERS;

COPPER CHLORIDE; ESTER; LACTAM; LACTONE; PAROXETINE;

ARTICLE; CATALYSIS; CHEMICAL ANALYSIS; COMPLEX FORMATION; CONJUGATION; ENANTIOSELECTIVITY; ESTERIFICATION; METHODOLOGY; STOICHIOMETRY;

ALCOHOLS; CATALYSIS; LACTAMS; LACTONES; MOLECULAR CONFORMATION; MOLECULAR STRUCTURE; OXIDATION-REDUCTION; PAROXETINE;

EID: 0042693206     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0351692     Document Type: Article

References (54)

1. For lead references regarding natural products containing chiral lactones, see: (a) Connolly, J. D.; Hill, R. A. Dictionary of Terpenoids; Chapman and Hall: London, 1991; Vol. 1, pp 476-541. (b) Peng, Z.-H.; Woerpel, K. A. Org. Lett. 2001, 3, 675 and references therein. (c) For synthetic approaches to Rolipram, see: Anada, M.; Mita, O.; Watanabe, H.; Kitagaki, S.; Hashimoto, S. Synlett 1999, 1775 and references therein.
2. For lead references regarding natural products containing chiral lactones, see: (a) Connolly, J. D.; Hill, R. A. Dictionary of Terpenoids; Chapman and Hall: London, 1991; Vol. 1, pp 476-541. (b) Peng, Z.-H.; Woerpel, K. A. Org. Lett. 2001, 3, 675 and references therein. (c) For synthetic approaches to Rolipram, see: Anada, M.; Mita, O.; Watanabe, H.; Kitagaki, S.; Hashimoto, S. Synlett 1999, 1775 and references therein.
3. For lead references regarding natural products containing chiral lactones, see: (a) Connolly, J. D.; Hill, R. A. Dictionary of Terpenoids; Chapman and Hall: London, 1991; Vol. 1, pp 476-541. (b) Peng, Z.-H.; Woerpel, K. A. Org. Lett. 2001, 3, 675 and references therein. (c) For synthetic approaches to Rolipram, see: Anada, M.; Mita, O.; Watanabe, H.; Kitagaki, S.; Hashimoto, S. Synlett 1999, 1775 and references therein.
4. For synthetic approaches to (-)-Paroxetine, see: (a) Christensen, J. A.; Squires, R. F. German Patent 2,404,113, 1974. U.S. Patent 3,912,743, 1975. U.S. Patent 4,007,196, 1977; Chem Abstr. 1974, 81, 152011q.
5. (b) Faruk, E. A.; Martin, R. T. EP Patent 223,334, 1986; Chem. Abstr. 1987, 107, 96594y.
6. (c) Yu, M. S.; Lantos, I.; Peng, Z.-Q.; Yu, J.; Cacchio, T. Tetrahedron Lett. 2000, 41. 5647.
7. (d) de Gonzalo, G.; Brieva, R.; Sánchez, V. M.; Bayod, M.; Gotor, V. J. Org. Chem. 2001, 66, 8947 and references therein. For a formal synthesis of (-)-Paroxetine, see ref 6.
8. For recent reviews of asymmetric conjugate addition, see: (a) Krause, N. ; Hoffmann-Röder, A. Synthesis 2001, 171.
9. (b) Sibi, M. P.; Manyem, S. Tetrahedron 2000, 56, 8033.
10. (a) Bella, M.; Piancatelli, G.; Pigro, M. C. Tetrahedron 1999, 55, 12387.
11. (b) Hollingworth, G. J.; Lee, T. V.; Sweeney, J. B. Synth. Commun. 1996, 26, 1117.
12. (c) Watanabe, M.; Tsukazaki, M.; Hirakawa, Y.; Iwao, M.; Furukawa, S. Chem. Pharm. Bull. 1989, 37, 2914.
13. (a) Tayaka, Y.; Senda, T.; Kurushima, H.; Ogasawara, M.; Hayashi, T. Tetrahedron: Assymetry 1999, 10, 4047. For catalytic enantioselective approaches to γ-lactones and γ-lactams having a β-stereocenter featuring Rh(II)-catalyzed intramolecular C-H insertions, see: (b) Bode, J. W.; Doyle, M. P.; Protopopova, M. N.; Zhou, Q.-L. J. Org. Chem. 1996, 61, 9146. (c) Anada, M.; Hashimoto, S. Tetrahedron Lett. 1998, 39, 79. See also ref Id.
14. (a) Tayaka, Y.; Senda, T.; Kurushima, H.; Ogasawara, M.; Hayashi, T. Tetrahedron: Assymetry 1999, 10, 4047. For catalytic enantioselective approaches to γ-lactones and γ-lactams having a β-stereocenter featuring Rh(II)-catalyzed intramolecular C-H insertions, see: (b) Bode, J. W.; Doyle, M. P.; Protopopova, M. N.; Zhou, Q.-L. J. Org. Chem. 1996, 61, 9146. (c) Anada, M.; Hashimoto, S. Tetrahedron Lett. 1998, 39, 79. See also ref Id.
15. (a) Tayaka, Y.; Senda, T.; Kurushima, H.; Ogasawara, M.; Hayashi, T. Tetrahedron: Assymetry 1999, 10, 4047. For catalytic enantioselective approaches to γ-lactones and γ-lactams having a β-stereocenter featuring Rh(II)-catalyzed intramolecular C-H insertions, see: (b) Bode, J. W.; Doyle, M. P.; Protopopova, M. N.; Zhou, Q.-L. J. Org. Chem. 1996, 61, 9146. (c) Anada, M.; Hashimoto, S. Tetrahedron Lett. 1998, 39, 79. See also ref Id.
16. Senda, T.; Ogasawara, M.; Hayashi, T. J. Org. Chem. 2001, 66, 6852.
17. (a) Reetz, M. T.; Gosberg, A.; Moulin, D. Tetrahedron Lett. 2002, 43, 1189.
18. (b) Kanai, M.; Nakagawa, Y.; Tomioka, K. Tetrahedron 1999, 55, 3843.
19. (c) Yan, M.; Zhou, Z.-Y.; Chan, A. J. Chem. Soc., Chem. Commun. 2000, 115.
20. (a) Appella, D. H.; Moritani, Y.; Shintani, R.; Ferreira, E. M.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 9473.
21. (b) Moritani, Y.; Appella, D. H.; Jurkauskas, V.; Buchwald, S. L. J. Am. Chem. Soc. 2000, 122, 6797.
22. (c) Jurkauskas, V.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 2892. Important related work: Lipshutz, B. H.; Papa, P. Angew. Chem., Int. Ed. 2002, 41, 4580.
23. (c) Jurkauskas, V.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 2892. Important related work: Lipshutz, B. H.; Papa, P. Angew. Chem., Int. Ed. 2002, 41, 4580.
24. After this manuscript was submitted, we became aware of prior work of Stryker. Specifically, he has reported three examples with three substrates in which the use of t-BuOH as an additive (10-15 equiv) allowed for the catalytic conjugate reduction to be carried out at 1 atm of hydrogen using 10-17 mol % Cu in 24-48 h. In the best case, the reduction of carvone is reduced to a 87:13 ratio of the conjugate reduction product and the overreduced saturated alcohol. The authors attribute the effect of the added t-BuOH to "a protolytic transfer process to quench the unstable intermediates with concomitant transfer of the copper to a more stable alkoxide moiety where hydrogen activation can proceed under lower pressure." Stryker has also demonstrated that the addition of t-BuOH often favors 1,2-reduction. (a) Lipshutz, B. H. In Modern Organocopper Chemistry; Krause, N., Ed.; Wiley-VCH: Weinheim, 2002; p 167. (b) Stryker, J. M.; Mahoney, W. S.; Daeuble, J. F.; Brestensky, D. M. In Catalysis in Organic Synthesis; Pascoe, W. E., Ed.; Marcel Dekker: New York, 1992; p 29. (c) Daeuble, J. F.; Stryker, J. M. In Catalysis of Organic Reactions; Scaros, M., Prunier, M. L., Eds.; Marcel Dekker: New York. 1995; p 235. (d) Chen, J. X. ; Daeuble, J. F.; Brestensky, D. M.; Stryker, J. M. Tetrahedron 2000, 56, 2153. (e) Chen, J. X.; Daeuble, D. M.; Stryker, J. M. Tetrahedron 2000, 56, 2789.
25. After this manuscript was submitted, we became aware of prior work of Stryker. Specifically, he has reported three examples with three substrates in which the use of t-BuOH as an additive (10-15 equiv) allowed for the catalytic conjugate reduction to be carried out at 1 atm of hydrogen using 10-17 mol % Cu in 24-48 h. In the best case, the reduction of carvone is reduced to a 87:13 ratio of the conjugate reduction product and the overreduced saturated alcohol. The authors attribute the effect of the added t-BuOH to "a protolytic transfer process to quench the unstable intermediates with concomitant transfer of the copper to a more stable alkoxide moiety where hydrogen activation can proceed under lower pressure." Stryker has also demonstrated that the addition of t-BuOH often favors 1,2-reduction. (a) Lipshutz, B. H. In Modern Organocopper Chemistry; Krause, N., Ed.; Wiley-VCH: Weinheim, 2002; p 167. (b) Stryker, J. M.; Mahoney, W. S.; Daeuble, J. F.; Brestensky, D. M. In Catalysis in Organic Synthesis; Pascoe, W. E., Ed.; Marcel Dekker: New York, 1992; p 29. (c) Daeuble, J. F.; Stryker, J. M. In Catalysis of Organic Reactions; Scaros, M., Prunier, M. L., Eds.; Marcel Dekker: New York. 1995; p 235. (d) Chen, J. X. ; Daeuble, J. F.; Brestensky, D. M.; Stryker, J. M. Tetrahedron 2000, 56, 2153. (e) Chen, J. X.; Daeuble, D. M.; Stryker, J. M. Tetrahedron 2000, 56, 2789.
26. After this manuscript was submitted, we became aware of prior work of Stryker. Specifically, he has reported three examples with three substrates in which the use of t-BuOH as an additive (10-15 equiv) allowed for the catalytic conjugate reduction to be carried out at 1 atm of hydrogen using 10-17 mol % Cu in 24-48 h. In the best case, the reduction of carvone is reduced to a 87:13 ratio of the conjugate reduction product and the overreduced saturated alcohol. The authors attribute the effect of the added t-BuOH to "a protolytic transfer process to quench the unstable intermediates with concomitant transfer of the copper to a more stable alkoxide moiety where hydrogen activation can proceed under lower pressure." Stryker has also demonstrated that the addition of t-BuOH often favors 1,2-reduction. (a) Lipshutz, B. H. In Modern Organocopper Chemistry; Krause, N., Ed.; Wiley-VCH: Weinheim, 2002; p 167. (b) Stryker, J. M.; Mahoney, W. S.; Daeuble, J. F.; Brestensky, D. M. In Catalysis in Organic Synthesis; Pascoe, W. E., Ed.; Marcel Dekker: New York, 1992; p 29. (c) Daeuble, J. F.; Stryker, J. M. In Catalysis of Organic Reactions; Scaros, M., Prunier, M. L., Eds.; Marcel Dekker: New York. 1995; p 235. (d) Chen, J. X. ; Daeuble, J. F.; Brestensky, D. M.; Stryker, J. M. Tetrahedron 2000, 56, 2153. (e) Chen, J. X.; Daeuble, D. M.; Stryker, J. M. Tetrahedron 2000, 56, 2789.
27. After this manuscript was submitted, we became aware of prior work of Stryker. Specifically, he has reported three examples with three substrates in which the use of t-BuOH as an additive (10-15 equiv) allowed for the catalytic conjugate reduction to be carried out at 1 atm of hydrogen using 10-17 mol % Cu in 24-48 h. In the best case, the reduction of carvone is reduced to a 87:13 ratio of the conjugate reduction product and the overreduced saturated alcohol. The authors attribute the effect of the added t-BuOH to "a protolytic transfer process to quench the unstable intermediates with concomitant transfer of the copper to a more stable alkoxide moiety where hydrogen activation can proceed under lower pressure." Stryker has also demonstrated that the addition of t-BuOH often favors 1,2-reduction. (a) Lipshutz, B. H. In Modern Organocopper Chemistry; Krause, N., Ed.; Wiley-VCH: Weinheim, 2002; p 167. (b) Stryker, J. M.; Mahoney, W. S.; Daeuble, J. F.; Brestensky, D. M. In Catalysis in Organic Synthesis; Pascoe, W. E., Ed.; Marcel Dekker: New York, 1992; p 29. (c) Daeuble, J. F.; Stryker, J. M. In Catalysis of Organic Reactions; Scaros, M., Prunier, M. L., Eds.; Marcel Dekker: New York. 1995; p 235. (d) Chen, J. X. ; Daeuble, J. F.; Brestensky, D. M.; Stryker, J. M. Tetrahedron 2000, 56, 2153. (e) Chen, J. X.; Daeuble, D. M.; Stryker, J. M. Tetrahedron 2000, 56, 2789.
28. After this manuscript was submitted, we became aware of prior work of Stryker. Specifically, he has reported three examples with three substrates in which the use of t-BuOH as an additive (10-15 equiv) allowed for the catalytic conjugate reduction to be carried out at 1 atm of hydrogen using 10-17 mol % Cu in 24-48 h. In the best case, the reduction of carvone is reduced to a 87:13 ratio of the conjugate reduction product and the overreduced saturated alcohol. The authors attribute the effect of the added t-BuOH to "a protolytic transfer process to quench the unstable intermediates with concomitant transfer of the copper to a more stable alkoxide moiety where hydrogen activation can proceed under lower pressure." Stryker has also demonstrated that the addition of t-BuOH often favors 1,2-reduction. (a) Lipshutz, B. H. In Modern Organocopper Chemistry; Krause, N., Ed.; Wiley-VCH: Weinheim, 2002; p 167. (b) Stryker, J. M.; Mahoney, W. S.; Daeuble, J. F.; Brestensky, D. M. In Catalysis in Organic Synthesis; Pascoe, W. E., Ed.; Marcel Dekker: New York, 1992; p 29. (c) Daeuble, J. F.; Stryker, J. M. In Catalysis of Organic Reactions; Scaros, M., Prunier, M. L., Eds.; Marcel Dekker: New York. 1995; p 235. (d) Chen, J. X. ; Daeuble, J. F.; Brestensky, D. M.; Stryker, J. M. Tetrahedron 2000, 56, 2153. (e) Chen, J. X.; Daeuble, D. M.; Stryker, J. M. Tetrahedron 2000, 56, 2789.
29. (a) Chatterjee, A. K.; Morgan, J. P.; Scholl, M.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 3783.
30. (b) Fürstner, A.; Thiel, O. R.; Ackermann, L.; Schanz, H.-J.; Nolan, S. P. J. Org. Chem. 2000, 65, 2204.
31. Buboudin, J. G.; Jousseaume, B. J. Organomet. Chem. 1979, 168, 1.
32. This behavior is suggestive of a catalyst decomposition pathway that is second order in Ru. For a discussion of the mechanism of Ru carbene decomposition pathways, see: Choi, T.-L.; Lee, C. W.; Chatterjee, A.; Grubbs. R. H. J. Am. Chem. Soc. 2001, 123, 10417.
33. (a) Bourguignon, J. J.; Wermuth, C. G. J. Org. Chem. 1981, 46, 4889.
34. (b) Bourguignon, J. J.; Schoenfelder, A.; Schmitt, M.; Wermuth, C. G.; Hechler, V.; Charlier, B.; Maitre, M. J. Med. Chem. 1988, 31, 893.
35. Trost, B. M.; Imi, K.; Davies, I. W. J. Am. Chem. Soc. 1995, 117, 5371.
36. (a) Barluenga, J.; Fañanás, F. J.; Foubelo, F.; Yus, M. Tetrahedron Lett. 1988, 29, 4859.
37. (b) Corriu, R. J. P.; Bolin, G.; Iqbal, J.; Moreau, J. J. E.; Vernhet, C. Tetrahedron 1993, 49, 4603.
38. (a) Klapers, A.; Huang, X.; Buchwald, S. L. J. Am. Chem. Soc. 2002. 124, 7421.
39. (b) Klapars, A.; Antilla, J. C.; Huang, X.; Buchwald, S. L. J. Am. Chem. Soc. 2001, 123, 7727.
40. For other examples of alcohols and amines accelerating metal-catalyzed silane reductions, see: (a) Verdaguer, X.; Lange, U. E. W.; Buchwald, S. L. Angew. Chem., Int. Ed. 1998, 37, 1103. (b) Yun, J.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 5640. (c) Hays, D. S.; Fu, G. C. Tetrahedron 1999, 55, 8815.
41. For other examples of alcohols and amines accelerating metal-catalyzed silane reductions, see: (a) Verdaguer, X.; Lange, U. E. W.; Buchwald, S. L. Angew. Chem., Int. Ed. 1998, 37, 1103. (b) Yun, J.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 5640. (c) Hays, D. S.; Fu, G. C. Tetrahedron 1999, 55, 8815.
42. For other examples of alcohols and amines accelerating metal-catalyzed silane reductions, see: (a) Verdaguer, X.; Lange, U. E. W.; Buchwald, S. L. Angew. Chem., Int. Ed. 1998, 37, 1103. (b) Yun, J.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 5640. (c) Hays, D. S.; Fu, G. C. Tetrahedron 1999, 55, 8815.
43. 2, was observed upon addition of EtOH.
44. Moritani, Y.; Fukushima, C.; Ukita, T.; Miyagishima, T.; Ohmizu, H.; Iwasaki, T. J. Org. Chem. 1996, 61, 6922.
45. It should be noted that the reduction of β-methyl substituted butenolide continues to suffer from poor mass balance, even under optimized conditions.
46. Hughes, G.; Buchwald, S. L., unpublished results. For related effects in catalytic enantioselective copper-hydride reductions of ketones, see: Sirol, S. ; Courarcel, J.; Mostefai, N.; Riant, O. Org. Lett. 2001, 3, 4111.
47. 2 and 10 equiv of t-BuONa per ligand, whereas an excess of Cu and base per ligand under anaerobic conditions was found to give poor conversions.
48. Huang, X.; Buchwald, S. L., unpublished results.
49. We presume that tosyl transfer occurs between 26 and 27 to produce a primary tosylate and a phenol, In the presence of base, the phenol displaces the primary tosylate to afford the desired coupling product. For similar examples of transfer of activation, see: (a) Sobolov, S, B.; Sun, J.; Cooper, B. A. Tetrahedron Lett. 1998, 39, 5685. (b) Kim, T. H.; Lee, G.-J. J. Org. Chem. 1999, 65, 2941.
50. We presume that tosyl transfer occurs between 26 and 27 to produce a primary tosylate and a phenol, In the presence of base, the phenol displaces the primary tosylate to afford the desired coupling product. For similar examples of transfer of activation, see: (a) Sobolov, S, B.; Sun, J.; Cooper, B. A. Tetrahedron Lett. 1998, 39, 5685. (b) Kim, T. H.; Lee, G.-J. J. Org. Chem. 1999, 65, 2941.
51. 13C NMR: Roeder, E.; Krauss, H. Liebigs Ann. Chem. 1992, 177. Optical rotation: Kosugi, H.; Tagami, K.; Takahashi, A.; Kanna, H.; Uda, H. J. Chem. Soc., Perkin Trans. 1 1989, 935.
52. 13C NMR: Roeder, E.; Krauss, H. Liebigs Ann. Chem. 1992, 177. Optical rotation: Kosugi, H.; Tagami, K.; Takahashi, A.; Kanna, H.; Uda, H. J. Chem. Soc., Perkin Trans. 1 1989, 935.
53. 13C NMR: Kayser, M. M.; Chen, G.; Stewart, J. D. J. Org. Chem. 1998, 63, 7103. Optical rotation: Jones, J. B.; Lok, K. P. Can. J. Chem. 1979, 57, 1025.
54. 13C NMR: Kayser, M. M.; Chen, G.; Stewart, J. D. J. Org. Chem. 1998, 63, 7103. Optical rotation: Jones, J. B.; Lok, K. P. Can. J. Chem. 1979, 57, 1025.