Asymmetric aminolysis of aromatic epoxides: A facile catalytic enantioselective synthesis of anti-β-amino alcohols

Organic Letters

Volumn 6, Issue 13, 2004, Pages 2173-2176

  Bartoli, Giuseppe ^a   Bosco, Marcella ^a   Carlone, Armando ^a   Locatelli, Manuela ^a   Massaccesi, Massimo ^a   Melchiorre, Paolo ^a   Sambri, Letizia ^a  

^a UNIVERSITY OF BOLOGNA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL; EPOXIDE;

ALCOHOL OXIDATION; AMINOLYSIS; ARTICLE; ASYMMETRIC CATALYSIS; CATALYSIS; CATALYST; CHIRALITY; ENANTIOSELECTIVITY; MANNICH REACTION; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 3142753508     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol049372t     Document Type: Article

References (33)

1. For reviews on the asymmetric synthesis and use of vicinal amino alcohols, see: (a) Bergmeier, S. C. Tetrahedron 2000, 56, 2561. (b) Ager, D. J.; Prakash, I.; Schaad, D. R. Chem. Rev. 1996, 96, 835. (c) Kolb, H. C.; Sharpless, K. B. In Transition Metals for Organic Synthesis; Beller, M., Bolm, C. Eds.; Wiley-VCH: Weinheim, 1998; p 243.
2. For reviews on the asymmetric synthesis and use of vicinal amino alcohols, see: (a) Bergmeier, S. C. Tetrahedron 2000, 56, 2561. (b) Ager, D. J.; Prakash, I.; Schaad, D. R. Chem. Rev. 1996, 96, 835. (c) Kolb, H. C.; Sharpless, K. B. In Transition Metals for Organic Synthesis; Beller, M., Bolm, C. Eds.; Wiley-VCH: Weinheim, 1998; p 243.
3. For reviews on the asymmetric synthesis and use of vicinal amino alcohols, see: (a) Bergmeier, S. C. Tetrahedron 2000, 56, 2561. (b) Ager, D. J.; Prakash, I.; Schaad, D. R. Chem. Rev. 1996, 96, 835. (c) Kolb, H. C.; Sharpless, K. B. In Transition Metals for Organic Synthesis; Beller, M., Bolm, C. Eds.; Wiley-VCH: Weinheim, 1998; p 243.
4. (a) Li, G.; Chang, H.-T.; Sharpless, K. B. Angew. Chem., Int. Ed. Engl. 1996, 35, 451.
5. (b) Review: O'Brien, P. Angew. Chem., Int. Ed. 1999, 38, 326.
6. (a) List, B. J. Am. Chem. Soc. 2000, 122, 9336.
7. (b) Córdova, A.; Notz, W.; Zhong, G.; Betancort, J. M.; Barbas, C. F., III. J. Am. Chem. Soc. 2002, 124, 1842.
8. (c) Trost, B. M.; Terrell, L. R. J. Am. Chem. Soc. 2003, 125, 338.
9. (4) (a) Kobayashi, S.; Hishitani, H.; Ueno, M. J. Am. Chem. Soc. 1998, 120, 431.
10. (b) Matsunaga, S.; Kumagai, N.; Harada, S.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 4712.
11. For examples about regioselective aminolysis of 1,2-disubstituted epoxides, see: (a) Caron, M.; Sharpless, K. B. J. Org. Chem. 1985, 50, 1557. (b) Chini, M.; Crotti, P.; Gardelli, C.; Macchia, F. J. Org. Chem. 1994, 59, 4131.
12. For examples about regioselective aminolysis of 1,2-disubstituted epoxides, see: (a) Caron, M.; Sharpless, K. B. J. Org. Chem. 1985, 50, 1557. (b) Chini, M.; Crotti, P.; Gardelli, C.; Macchia, F. J. Org. Chem. 1994, 59, 4131.
13. Moderate enantioselective ring opening with anilines has been reported only with meso-epoxides; see: (a) Hou, X.-L.; Wu, J.; Dai, L.-X.; Xia, L.-J.; Tang, M.-H. Tetrahedron: Asymmetry 1998, 9, 1747. (b) Sekar, G.; Kamble, R. M.; Singh, V. K. Tetrahedron: Asymmetry 1999, 10, 3663.
14. Moderate enantioselective ring opening with anilines has been reported only with meso-epoxides; see: (a) Hou, X.-L.; Wu, J.; Dai, L.-X.; Xia, L.-J.; Tang, M.-H. Tetrahedron: Asymmetry 1998, 9, 1747. (b) Sekar, G.; Kamble, R. M.; Singh, V. K. Tetrahedron: Asymmetry 1999, 10, 3663.
15. Highly enantioselective ring opening with azide has been reported only with meso- and terminal epoxides. meso-Epoxides, see: (a) Martinez, L. E.; Leighton, J. L.; Carsten, D. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5897. (b) Nugent, W. A. J. Am. Chem. Soc. 1992, 114, 2768. Terminal epoxides, see: (c) Larrow, J. F.; Schaus, S. E.; Jacobsen, E. N. J. Am. Chem. Soc. 1996, 118, 7420. Review: (d) Jacobsen, E. N.; Wu, M. H. In Comprehensive Asymmetric Catalysis I-III, Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Chapter 35.
16. Highly enantioselective ring opening with azide has been reported only with meso- and terminal epoxides. meso-Epoxides, see: (a) Martinez, L. E.; Leighton, J. L.; Carsten, D. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5897. (b) Nugent, W. A. J. Am. Chem. Soc. 1992, 114, 2768. Terminal epoxides, see: (c) Larrow, J. F.; Schaus, S. E.; Jacobsen, E. N. J. Am. Chem. Soc. 1996, 118, 7420. Review: (d) Jacobsen, E. N.; Wu, M. H. In Comprehensive Asymmetric Catalysis I-III, Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Chapter 35.
17. Highly enantioselective ring opening with azide has been reported only with meso- and terminal epoxides. meso-Epoxides, see: (a) Martinez, L. E.; Leighton, J. L.; Carsten, D. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5897. (b) Nugent, W. A. J. Am. Chem. Soc. 1992, 114, 2768. Terminal epoxides, see: (c) Larrow, J. F.; Schaus, S. E.; Jacobsen, E. N. J. Am. Chem. Soc. 1996, 118, 7420. Review: (d) Jacobsen, E. N.; Wu, M. H. In Comprehensive Asymmetric Catalysis I-III, Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Chapter 35.
18. Highly enantioselective ring opening with azide has been reported only with meso- and terminal epoxides. meso-Epoxides, see: (a) Martinez, L. E.; Leighton, J. L.; Carsten, D. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5897. (b) Nugent, W. A. J. Am. Chem. Soc. 1992, 114, 2768. Terminal epoxides, see: (c) Larrow, J. F.; Schaus, S. E.; Jacobsen, E. N. J. Am. Chem. Soc. 1996, 118, 7420. Review: (d) Jacobsen, E. N.; Wu, M. H. In Comprehensive Asymmetric Catalysis I-III, Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Chapter 35.
19. (a) Bandini, M.; Cozzi, P. G.; Melchiorre, P.; Umani-Ronchi, A. Angew. Chem., Int. Ed. 2004, 43, 84. For a review, see: (b) Jacobsen, E. N. Acc. Chem. Res. 2000, 33, 421. See also refs 7a and 7c.
20. (a) Bandini, M.; Cozzi, P. G.; Melchiorre, P.; Umani-Ronchi, A. Angew. Chem., Int. Ed. 2004, 43, 84. For a review, see: (b) Jacobsen, E. N. Acc. Chem. Res. 2000, 33, 421. See also refs 7a and 7c.
21. The use of different chiral catalysts (e.g., Co(III)-(Salen) complexes) and aliphatic amines (e.g., pyrrolidine) resulted in no reaction.
22. Keith, J. M.; Larrow, J. F.; Jacobsen, E. N. Adv. Synth. Catal. 2001, 343, 5.
23. The selectivity factors s were calculated using the equation s = ln[1 - c(1 + ee)]/ln[1 - c(1 - ee)], where ee is the enantiomeric excess of the amino alcohol product and c is the conversion; see Supporting Information for details.
24. (a) Keck, G. E.; Truong, A. P. Org. Lett. 2002, 4, 3131.
25. (b) Kronenthal, D. R.; Han, C. Y.; Taylor, M. K. J. Org. Chem. 1982, 47, 2765.
26. It has been shown that an aromatic substituent on the oxirane ring usually promotes the ring opening on the adjacent carbon: Jaime, C.; Ortuño, R. M.; Font, J. J. Org. Chem. 1988, 53, 139. For a similar regioselectivity in [Cr(Salen)Cl]-catalyzed kinetic resolution of 1,2-disubstituted aromatic epoxides, see ref 8a.
27. In all cases, only the anti-diastereomer and a single regioisomer was detected by NMR and HPLC analysis. The relative stereochemistry was established through NOE studies on the corresponding cyclic carbamates; see Supporting Information for details.
28. The absolute configuration of 4b was established after conversion in the corresponding cyclic carbamate and subsequent CAN-promoted dearylation and by comparison of the optical rotation with an authentic sample. For products 6 the absolute configuration was assigned by analogy; see Supporting Information for details.
29. Thomas, A. A.; Sharpless, K. B. J. Org. Chem. 1999, 64, 8379 and references therein.
30. The AKR of cis-1,2-disubstituted aromatic epoxides (i.e., naphthalene oxide and cis-β-methyl-styrene oxide) afforded the syn-β-amino alcohols with complete regio- and diastereocontrol but in low enantiomeric excess (less than 40% ee).
31. Plot of catalyst ee vs product ee is provided in Supporting Information.
32. For similar observations about NLE in other [Cr(Salen)Cl]-catalyzed asymmetric ring opening of epoxides, see: (a) Hansen, K. B.; Leighton, J. L.; Jacobsen, E. N. J. Am. Chem. Soc. 1996, 118, 10924. For an excellent review about nonlinear effects, see: (b) Girard, C.; Kagan, H. B. Angew. Chem., Int. Ed. 1998, 37, 2922.
33. For similar observations about NLE in other [Cr(Salen)Cl]-catalyzed asymmetric ring opening of epoxides, see: (a) Hansen, K. B.; Leighton, J. L.; Jacobsen, E. N. J. Am. Chem. Soc. 1996, 118, 10924. For an excellent review about nonlinear effects, see: (b) Girard, C.; Kagan, H. B. Angew. Chem., Int. Ed. 1998, 37, 2922.