Enantiospecific synthesis of allylamines via the regioselective rhodium- catalyzed allylic amination reaction [8]

Journal of the American Chemical Society

Volumn 121, Issue 28, 1999, Pages 6761-6762

  Evans, P Andrew ^a   Robinson, John E ^a   Nelson, Jade D ^a  

^a UNIVERSITY OF DELAWARE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYLAMINE; AMINOALCOHOL; CARBONIC ACID DERIVATIVE;

AMINATION; CATALYSIS; CATALYST; CHEMICAL STRUCTURE; ENANTIOMER; LETTER; REACTION ANALYSIS; SYNTHESIS;

EID: 0033591863     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991089f     Document Type: Letter

References (29)

1. For a recent review on allylic amination, see: Johannsen, M.; Jørgensen, K. A. Chem. Rev. 1998, 98, 1689 and references therein. For a recent example of an enantioselective approach to allylamines, see: Donde, Y.; Overman, L. E. J. Am. Chem. Soc. 1999, 121, 2933.
2. For a recent review on allylic amination, see: Johannsen, M.; Jørgensen, K. A. Chem. Rev. 1998, 98, 1689 and references therein. For a recent example of an enantioselective approach to allylamines, see: Donde, Y.; Overman, L. E. J. Am. Chem. Soc. 1999, 121, 2933.
3. 3-intermediates, see: (a) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (b) Togni, A.; Burckhardt, U.; Gramlich, V.; Pregosin, P. S.; Salzmann, T. J. Am. Chem. Soc. 1996, 118, 1031. (c) Burckhardt, U.; Baumann, M.; Trabesinger, G.; Gramlich, V.; Togni, A. Organometallics 1997, 16, 5252. (d) Trost, B. M.; Bunt, R. C J. Am. Chem. Soc. 1994, 116, 4089. (e) Trost, B. M.; Radinov, R. J. Am. Chem. Soc. 1997, 119, 5962 and references therein.
4. 3-intermediates, see: (a) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (b) Togni, A.; Burckhardt, U.; Gramlich, V.; Pregosin, P. S.; Salzmann, T. J. Am. Chem. Soc. 1996, 118, 1031. (c) Burckhardt, U.; Baumann, M.; Trabesinger, G.; Gramlich, V.; Togni, A. Organometallics 1997, 16, 5252. (d) Trost, B. M.; Bunt, R. C J. Am. Chem. Soc. 1994, 116, 4089. (e) Trost, B. M.; Radinov, R. J. Am. Chem. Soc. 1997, 119, 5962 and references therein.
5. 3-intermediates, see: (a) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (b) Togni, A.; Burckhardt, U.; Gramlich, V.; Pregosin, P. S.; Salzmann, T. J. Am. Chem. Soc. 1996, 118, 1031. (c) Burckhardt, U.; Baumann, M.; Trabesinger, G.; Gramlich, V.; Togni, A. Organometallics 1997, 16, 5252. (d) Trost, B. M.; Bunt, R. C J. Am. Chem. Soc. 1994, 116, 4089. (e) Trost, B. M.; Radinov, R. J. Am. Chem. Soc. 1997, 119, 5962 and references therein.
6. 3-intermediates, see: (a) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (b) Togni, A.; Burckhardt, U.; Gramlich, V.; Pregosin, P. S.; Salzmann, T. J. Am. Chem. Soc. 1996, 118, 1031. (c) Burckhardt, U.; Baumann, M.; Trabesinger, G.; Gramlich, V.; Togni, A. Organometallics 1997, 16, 5252. (d) Trost, B. M.; Bunt, R. C J. Am. Chem. Soc. 1994, 116, 4089. (e) Trost, B. M.; Radinov, R. J. Am. Chem. Soc. 1997, 119, 5962 and references therein.
7. 3-intermediates, see: (a) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (b) Togni, A.; Burckhardt, U.; Gramlich, V.; Pregosin, P. S.; Salzmann, T. J. Am. Chem. Soc. 1996, 118, 1031. (c) Burckhardt, U.; Baumann, M.; Trabesinger, G.; Gramlich, V.; Togni, A. Organometallics 1997, 16, 5252. (d) Trost, B. M.; Bunt, R. C J. Am. Chem. Soc. 1994, 116, 4089. (e) Trost, B. M.; Radinov, R. J. Am. Chem. Soc. 1997, 119, 5962 and references therein.
8. For leading references to transition metal-catalyzed allylic amination using racemic vinyl epoxides, see: Trost, B. M.; Bunt, R. C. Angew Chem., Int. Ed. Engl. 1996, 35, 99.
9. (a) Evans, P. A.; Nelson, J. D. Tetrahedron Lett. 1998, 38, 1725.
10. (b) Evans, P. A.; Nelson, J. D. J. Am. Chem. Soc. 1998, 120, 5581.
11. Enyl complexes can be defined as those having a discrete σ- and π-metal carbon component within a single ligand. For definitions and examples, see: (a) Sharp P. R. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: New York, 1995, Chapter 2, p 272. (b) Lawson, D. N.; Osborn, J. A.; Wilkinson, G. J. Chem. Soc. (A) 1966, 1733. (c) Tanaka, I.; Jin-no, N.; Kushida, T.; Tsutsui, N.; Ashida, T.; Suzuki, H.; Sakurai, H.; Moro-oka, Y.; Ikawa, T. Bull. Chem. Soc. Jpn. 1983, 56, 657 and references therein.
12. Enyl complexes can be defined as those having a discrete σ- and π-metal carbon component within a single ligand. For definitions and examples, see: (a) Sharp P. R. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: New York, 1995, Chapter 2, p 272. (b) Lawson, D. N.; Osborn, J. A.; Wilkinson, G. J. Chem. Soc. (A) 1966, 1733. (c) Tanaka, I.; Jin-no, N.; Kushida, T.; Tsutsui, N.; Ashida, T.; Suzuki, H.; Sakurai, H.; Moro-oka, Y.; Ikawa, T. Bull. Chem. Soc. Jpn. 1983, 56, 657 and references therein.
13. Enyl complexes can be defined as those having a discrete σ- and π-metal carbon component within a single ligand. For definitions and examples, see: (a) Sharp P. R. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: New York, 1995, Chapter 2, p 272. (b) Lawson, D. N.; Osborn, J. A.; Wilkinson, G. J. Chem. Soc. (A) 1966, 1733. (c) Tanaka, I.; Jin-no, N.; Kushida, T.; Tsutsui, N.; Ashida, T.; Suzuki, H.; Sakurai, H.; Moro-oka, Y.; Ikawa, T. Bull. Chem. Soc. Jpn. 1983, 56, 657 and references therein.
14. 2NH.; 4a/b = 1:9) provided homogeneous reaction mixtures that furnished the allylic amination adducts with improved regioselectivity. However, despite the improved selectivity the poor turnover rates and modest yields of 4a/b deemed them unsuitable for preparative work, which was presumably due to competitive coordination of the nucleophile with the metal center. The crossover in regioselectivity for these nucleophiles is also rather interesting, and most likely a steric effect. (figure presented)
15. The term conservation of enantiomeric excess {cee = (product ee/starting material ee) × 100} provides a convenient method of describing the enantiopecificity of the reaction
16. The loss in enantiopurity for the conversion of 1a to 2a is not specific to this substrate, and was observed with other carbonates of similar enantiomeric purity (96% ee).
17. The retention of absolute configuration in the rhodium-catalyzed amination, was assigned on the conversion of allylic carbonate 1e to (R)-homophenylalanine, as outlined in Scheme 1.
18. 4), filtered, and concentrated in vacuo to afford a crude oil. Purification by flash chromatography (eluting with a 5-15% ethyl acetate/hexane gradient) furnished the allylic animation product 2i (0.193 g, 90%) as a straw-colored oil, with ≥99% ee by chiral HPLC analysis using a CHIRALCEL OD column.
19. The enantiomerically enriched allylic alcohols were prepared using the Sharpless asymmetric kinetic resolution of the racemic allylic alcohol derivatives with dicyclohexyl tartrate; see: Gao, Y.; Hanson, R. M.; Klunder, J. M.; Ko, S. Y.; Masamune, H.; Sharpless, K. B. J. Am. Chem. Soc. 1987, 109, 5765.
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22. For a recent review on the asymmetric synthesis of α-amino acids, see: Davis, F. A.; Zhou, P.; Chen, B. C. Chem. Soc. Rev. 1998, 27, 13.
23. For recent examples of asymmetric approaches to α-amino acids, see: (a) Corey, E. J.; Link, J. O. J. Am. Chem. Soc. 1992, 114, 1906. (b) Petasis, N. A.; Zavialov, I. A. J. Am. Chem. Soc. 1997, 119, 445. (c) Drury, W. J., III.; Ferraris, D.; Cox, C.; Young, B.; Lectka, T. J. Am. Chem. Soc. 1998, 120, 11006. (d) Krueger, C. A.; Kuntz, K. W.; Dzierba, C. D.; Wirschun, W. G.; Gleason, J. D.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 4284. (e) Tunge, J. A.; Gately, D. A.; Norton, J. R. J. Am. Chem. Soc. 1999, 121, 4520 and references therein.
24. For recent examples of asymmetric approaches to α-amino acids, see: (a) Corey, E. J.; Link, J. O. J. Am. Chem. Soc. 1992, 114, 1906. (b) Petasis, N. A.; Zavialov, I. A. J. Am. Chem. Soc. 1997, 119, 445. (c) Drury, W. J., III.; Ferraris, D.; Cox, C.; Young, B.; Lectka, T. J. Am. Chem. Soc. 1998, 120, 11006. (d) Krueger, C. A.; Kuntz, K. W.; Dzierba, C. D.; Wirschun, W. G.; Gleason, J. D.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 4284. (e) Tunge, J. A.; Gately, D. A.; Norton, J. R. J. Am. Chem. Soc. 1999, 121, 4520 and references therein.
25. For recent examples of asymmetric approaches to α-amino acids, see: (a) Corey, E. J.; Link, J. O. J. Am. Chem. Soc. 1992, 114, 1906. (b) Petasis, N. A.; Zavialov, I. A. J. Am. Chem. Soc. 1997, 119, 445. (c) Drury, W. J., III.; Ferraris, D.; Cox, C.; Young, B.; Lectka, T. J. Am. Chem. Soc. 1998, 120, 11006. (d) Krueger, C. A.; Kuntz, K. W.; Dzierba, C. D.; Wirschun, W. G.; Gleason, J. D.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 4284. (e) Tunge, J. A.; Gately, D. A.; Norton, J. R. J. Am. Chem. Soc. 1999, 121, 4520 and references therein.
26. For recent examples of asymmetric approaches to α-amino acids, see: (a) Corey, E. J.; Link, J. O. J. Am. Chem. Soc. 1992, 114, 1906. (b) Petasis, N. A.; Zavialov, I. A. J. Am. Chem. Soc. 1997, 119, 445. (c) Drury, W. J., III.; Ferraris, D.; Cox, C.; Young, B.; Lectka, T. J. Am. Chem. Soc. 1998, 120, 11006. (d) Krueger, C. A.; Kuntz, K. W.; Dzierba, C. D.; Wirschun, W. G.; Gleason, J. D.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 4284. (e) Tunge, J. A.; Gately, D. A.; Norton, J. R. J. Am. Chem. Soc. 1999, 121, 4520 and references therein.
27. For recent examples of asymmetric approaches to α-amino acids, see: (a) Corey, E. J.; Link, J. O. J. Am. Chem. Soc. 1992, 114, 1906. (b) Petasis, N. A.; Zavialov, I. A. J. Am. Chem. Soc. 1997, 119, 445. (c) Drury, W. J., III.; Ferraris, D.; Cox, C.; Young, B.; Lectka, T. J. Am. Chem. Soc. 1998, 120, 11006. (d) Krueger, C. A.; Kuntz, K. W.; Dzierba, C. D.; Wirschun, W. G.; Gleason, J. D.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 4284. (e) Tunge, J. A.; Gately, D. A.; Norton, J. R. J. Am. Chem. Soc. 1999, 121, 4520 and references therein.
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29. For a recent review on ring-closing metathesis, see: Grubbs, R. H. Tetrahedron 1998, 54, 4413.