Highly regioselective hydrogenolysis of bis(α-methylbenzyl)amine derivatives affected by the trifluoromethyl substituent on the aromatic ring

Organic Letters

Volumn 5, Issue 7, 2003, Pages 1007-1010

  Kanai, Masatomi ^a   Yasumoto, Manabu ^a   Kuriyama, Yokusu ^a   Inomiya, Kenjin ^a   Katsuhara, Yutaka ^a   Higashiyama, Kimio ^b   Ishii, Akihiro ^a  

^a CENTRAL GLASS CO LTD   (Japan)

^b HOSHI UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; AROMATIC COMPOUND; METHYL GROUP;

ARTICLE; ASYMMETRIC SYNTHESIS; CHEMICAL REACTION; ELECTRONICS; HYDROGENOLYSIS; STEREOCHEMISTRY;

EID: 0141630303     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol034014w     Document Type: Article

References (29)

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6. In these cases, the steric effect could not be completely excluded due to the proximity to the benzylic carbon-nitrogen bond to confuse the estimation of the electronic effect. (a) Bringmann, G.; Geisler, J.-P. J. Fluorine Chem. 1990, 49, 67. (b) Bringmann, G. DE 3819438, 1989.
7. In these cases, the steric effect could not be completely excluded due to the proximity to the benzylic carbon-nitrogen bond to confuse the estimation of the electronic effect. (a) Bringmann, G.; Geisler, J.-P. J. Fluorine Chem. 1990, 49, 67. (b) Bringmann, G. DE 3819438, 1989.
8. Trifluoromethyl-substituted α-phenylethylamines have been regarded as important intermediates in the development of medicines. (a) Alvaro, G.; Di Fabio, R.; Giovannini, R.; Guercio, G.; St-Denis, Y.; Ursini, A. WO 0125219, 2001. (b) Armstrong, H. M.; Beresis, R.; Goulet, J. L.; Holmes, M. A.; Hong, X. ; Mills, S. G.; Parsons, W. H.; Sinclair, P. J.; Steiner, M. G.; Wong, F.; Zaller, D. M. WO 0100213, 2001. (c) Bloom, J. D.; Digrandi, M. J.; Dushin, R. G.; Lang, S. A.; O'Hara, B. M. WO 0034269, 2000. From an industrial point of view, our synthetic method is very practical, because enantiomerically pure (>99.5% ee) trifluoromethyl-substituted α-phenylethylamines are easily prepared in an acceptable yield. Recently, the enantioselective hydrogenation of enamides or phosphinylimines using a catalytic amount of Rh catalysts containing various chiral phosphine ligands has been studied. However, the optical purity of the obtained acetamides or phosphinamides was insufficient, and a sequential tedious hydrolysis of the resulting hydrogenated products followed. (a) Spindler, F.; Blaser H.-U. Adv. Synth. Catal. 2001, 343, 68. (b) Hu, W.; Yan. M.; Lau, C.-P.; Yang, S. M.; Chan, A. S. C.; Jiang, Y.; Mi, A. Tetrahedron Lett. 1999, 40, 973. (c) Zhang, F.-Y.; Pai, C.-C.; Chan, A. S. C. J. Am. Chem. Soc. 1998, 120, 5808. (d) Burk, M. J.; Wang, Y. M.; Lee, J. R. J. Am. Chem. Soc. 1996, 118, 5142.
9. Trifluoromethyl-substituted α-phenylethylamines have been regarded as important intermediates in the development of medicines. (a) Alvaro, G.; Di Fabio, R.; Giovannini, R.; Guercio, G.; St-Denis, Y.; Ursini, A. WO 0125219, 2001. (b) Armstrong, H. M.; Beresis, R.; Goulet, J. L.; Holmes, M. A.; Hong, X. ; Mills, S. G.; Parsons, W. H.; Sinclair, P. J.; Steiner, M. G.; Wong, F.; Zaller, D. M. WO 0100213, 2001. (c) Bloom, J. D.; Digrandi, M. J.; Dushin, R. G.; Lang, S. A.; O'Hara, B. M. WO 0034269, 2000. From an industrial point of view, our synthetic method is very practical, because enantiomerically pure (>99.5% ee) trifluoromethyl-substituted α-phenylethylamines are easily prepared in an acceptable yield. Recently, the enantioselective hydrogenation of enamides or phosphinylimines using a catalytic amount of Rh catalysts containing various chiral phosphine ligands has been studied. However, the optical purity of the obtained acetamides or phosphinamides was insufficient, and a sequential tedious hydrolysis of the resulting hydrogenated products followed. (a) Spindler, F.; Blaser H.-U. Adv. Synth. Catal. 2001, 343, 68. (b) Hu, W.; Yan. M.; Lau, C.-P.; Yang, S. M.; Chan, A. S. C.; Jiang, Y.; Mi, A. Tetrahedron Lett. 1999, 40, 973. (c) Zhang, F.-Y.; Pai, C.-C.; Chan, A. S. C. J. Am. Chem. Soc. 1998, 120, 5808. (d) Burk, M. J.; Wang, Y. M.; Lee, J. R. J. Am. Chem. Soc. 1996, 118, 5142.
10. Trifluoromethyl-substituted α-phenylethylamines have been regarded as important intermediates in the development of medicines. (a) Alvaro, G.; Di Fabio, R.; Giovannini, R.; Guercio, G.; St-Denis, Y.; Ursini, A. WO 0125219, 2001. (b) Armstrong, H. M.; Beresis, R.; Goulet, J. L.; Holmes, M. A.; Hong, X. ; Mills, S. G.; Parsons, W. H.; Sinclair, P. J.; Steiner, M. G.; Wong, F.; Zaller, D. M. WO 0100213, 2001. (c) Bloom, J. D.; Digrandi, M. J.; Dushin, R. G.; Lang, S. A.; O'Hara, B. M. WO 0034269, 2000. From an industrial point of view, our synthetic method is very practical, because enantiomerically pure (>99.5% ee) trifluoromethyl-substituted α-phenylethylamines are easily prepared in an acceptable yield. Recently, the enantioselective hydrogenation of enamides or phosphinylimines using a catalytic amount of Rh catalysts containing various chiral phosphine ligands has been studied. However, the optical purity of the obtained acetamides or phosphinamides was insufficient, and a sequential tedious hydrolysis of the resulting hydrogenated products followed. (a) Spindler, F.; Blaser H.-U. Adv. Synth. Catal. 2001, 343, 68. (b) Hu, W.; Yan. M.; Lau, C.-P.; Yang, S. M.; Chan, A. S. C.; Jiang, Y.; Mi, A. Tetrahedron Lett. 1999, 40, 973. (c) Zhang, F.-Y.; Pai, C.-C.; Chan, A. S. C. J. Am. Chem. Soc. 1998, 120, 5808. (d) Burk, M. J.; Wang, Y. M.; Lee, J. R. J. Am. Chem. Soc. 1996, 118, 5142.
11. Trifluoromethyl-substituted α-phenylethylamines have been regarded as important intermediates in the development of medicines. (a) Alvaro, G.; Di Fabio, R.; Giovannini, R.; Guercio, G.; St-Denis, Y.; Ursini, A. WO 0125219, 2001. (b) Armstrong, H. M.; Beresis, R.; Goulet, J. L.; Holmes, M. A.; Hong, X. ; Mills, S. G.; Parsons, W. H.; Sinclair, P. J.; Steiner, M. G.; Wong, F.; Zaller, D. M. WO 0100213, 2001. (c) Bloom, J. D.; Digrandi, M. J.; Dushin, R. G.; Lang, S. A.; O'Hara, B. M. WO 0034269, 2000. From an industrial point of view, our synthetic method is very practical, because enantiomerically pure (>99.5% ee) trifluoromethyl-substituted α-phenylethylamines are easily prepared in an acceptable yield. Recently, the enantioselective hydrogenation of enamides or phosphinylimines using a catalytic amount of Rh catalysts containing various chiral phosphine ligands has been studied. However, the optical purity of the obtained acetamides or phosphinamides was insufficient, and a sequential tedious hydrolysis of the resulting hydrogenated products followed. (a) Spindler, F.; Blaser H.-U. Adv. Synth. Catal. 2001, 343, 68. (b) Hu, W.; Yan. M.; Lau, C.-P.; Yang, S. M.; Chan, A. S. C.; Jiang, Y.; Mi, A. Tetrahedron Lett. 1999, 40, 973. (c) Zhang, F.-Y.; Pai, C.-C.; Chan, A. S. C. J. Am. Chem. Soc. 1998, 120, 5808. (d) Burk, M. J.; Wang, Y. M.; Lee, J. R. J. Am. Chem. Soc. 1996, 118, 5142.
12. Trifluoromethyl-substituted α-phenylethylamines have been regarded as important intermediates in the development of medicines. (a) Alvaro, G.; Di Fabio, R.; Giovannini, R.; Guercio, G.; St-Denis, Y.; Ursini, A. WO 0125219, 2001. (b) Armstrong, H. M.; Beresis, R.; Goulet, J. L.; Holmes, M. A.; Hong, X. ; Mills, S. G.; Parsons, W. H.; Sinclair, P. J.; Steiner, M. G.; Wong, F.; Zaller, D. M. WO 0100213, 2001. (c) Bloom, J. D.; Digrandi, M. J.; Dushin, R. G.; Lang, S. A.; O'Hara, B. M. WO 0034269, 2000. From an industrial point of view, our synthetic method is very practical, because enantiomerically pure (>99.5% ee) trifluoromethyl-substituted α-phenylethylamines are easily prepared in an acceptable yield. Recently, the enantioselective hydrogenation of enamides or phosphinylimines using a catalytic amount of Rh catalysts containing various chiral phosphine ligands has been studied. However, the optical purity of the obtained acetamides or phosphinamides was insufficient, and a sequential tedious hydrolysis of the resulting hydrogenated products followed. (a) Spindler, F.; Blaser H.-U. Adv. Synth. Catal. 2001, 343, 68. (b) Hu, W.; Yan. M.; Lau, C.-P.; Yang, S. M.; Chan, A. S. C.; Jiang, Y.; Mi, A. Tetrahedron Lett. 1999, 40, 973. (c) Zhang, F.-Y.; Pai, C.-C.; Chan, A. S. C. J. Am. Chem. Soc. 1998, 120, 5808. (d) Burk, M. J.; Wang, Y. M.; Lee, J. R. J. Am. Chem. Soc. 1996, 118, 5142.
13. Trifluoromethyl-substituted α-phenylethylamines have been regarded as important intermediates in the development of medicines. (a) Alvaro, G.; Di Fabio, R.; Giovannini, R.; Guercio, G.; St-Denis, Y.; Ursini, A. WO 0125219, 2001. (b) Armstrong, H. M.; Beresis, R.; Goulet, J. L.; Holmes, M. A.; Hong, X. ; Mills, S. G.; Parsons, W. H.; Sinclair, P. J.; Steiner, M. G.; Wong, F.; Zaller, D. M. WO 0100213, 2001. (c) Bloom, J. D.; Digrandi, M. J.; Dushin, R. G.; Lang, S. A.; O'Hara, B. M. WO 0034269, 2000. From an industrial point of view, our synthetic method is very practical, because enantiomerically pure (>99.5% ee) trifluoromethyl-substituted α-phenylethylamines are easily prepared in an acceptable yield. Recently, the enantioselective hydrogenation of enamides or phosphinylimines using a catalytic amount of Rh catalysts containing various chiral phosphine ligands has been studied. However, the optical purity of the obtained acetamides or phosphinamides was insufficient, and a sequential tedious hydrolysis of the resulting hydrogenated products followed. (a) Spindler, F.; Blaser H.-U. Adv. Synth. Catal. 2001, 343, 68. (b) Hu, W.; Yan. M.; Lau, C.-P.; Yang, S. M.; Chan, A. S. C.; Jiang, Y.; Mi, A. Tetrahedron Lett. 1999, 40, 973. (c) Zhang, F.-Y.; Pai, C.-C.; Chan, A. S. C. J. Am. Chem. Soc. 1998, 120, 5808. (d) Burk, M. J.; Wang, Y. M.; Lee, J. R. J. Am. Chem. Soc. 1996, 118, 5142.
14. Trifluoromethyl-substituted α-phenylethylamines have been regarded as important intermediates in the development of medicines. (a) Alvaro, G.; Di Fabio, R.; Giovannini, R.; Guercio, G.; St-Denis, Y.; Ursini, A. WO 0125219, 2001. (b) Armstrong, H. M.; Beresis, R.; Goulet, J. L.; Holmes, M. A.; Hong, X. ; Mills, S. G.; Parsons, W. H.; Sinclair, P. J.; Steiner, M. G.; Wong, F.; Zaller, D. M. WO 0100213, 2001. (c) Bloom, J. D.; Digrandi, M. J.; Dushin, R. G.; Lang, S. A.; O'Hara, B. M. WO 0034269, 2000. From an industrial point of view, our synthetic method is very practical, because enantiomerically pure (>99.5% ee) trifluoromethyl-substituted α-phenylethylamines are easily prepared in an acceptable yield. Recently, the enantioselective hydrogenation of enamides or phosphinylimines using a catalytic amount of Rh catalysts containing various chiral phosphine ligands has been studied. However, the optical purity of the obtained acetamides or phosphinamides was insufficient, and a sequential tedious hydrolysis of the resulting hydrogenated products followed. (a) Spindler, F.; Blaser H.-U. Adv. Synth. Catal. 2001, 343, 68. (b) Hu, W.; Yan. M.; Lau, C.-P.; Yang, S. M.; Chan, A. S. C.; Jiang, Y.; Mi, A. Tetrahedron Lett. 1999, 40, 973. (c) Zhang, F.-Y.; Pai, C.-C.; Chan, A. S. C. J. Am. Chem. Soc. 1998, 120, 5808. (d) Burk, M. J.; Wang, Y. M.; Lee, J. R. J. Am. Chem. Soc. 1996, 118, 5142.
15. 3-3. The ratio of 19:40:41 in three isomers changed to that of 25:48:27 after 2 h at 120°C.
16. 2/C as a Pd catalyst for a longer reaction time.
17. 3-3 was prepared by the recrystallization of the fumaric acid salt instead of the p-TsOH salt in ca. 60% recovery yield.
18. Compound 5 was prepared in quantitative yield from 3,5-bis-(trifluoromethyl)benzaldehyde and benzylamine in a similar manner.
19. 3-3 in >95% isolated yield.
20. 3-1 and (R)-phenylglycinol in a similar manner. The regioselective hydrogenolysis was carried out using the diastereomeric mixture of 7 (14% de).
21. Gaunt, M. J.; Yu, J.; Spencer, J. B. J. Org. Chem. 1998, 63, 4172.
22. Fluorine would most closely resemble and mimic hydrogen in bioactive compounds with respect to steric requirements at the enzyme receptor. Filler, R. In Organofluorine Chemicals and Their Industrial Applications; Banks, R. E., Ed.; Ellis Horwood, Ltd.: Chichester, UK, 1979; Chapter 6.
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25. (c) Nagai, T.; Nishioka, G.; Koyama, M.; Ando, A.; Miki, T.; Kumadaki, I. J. Fluorine Chem. 1992, 57, 229.
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28. Hydrogenolysis of bis(α-methylbenzyl)amine derivative (9) having a 4-tert-butyl monosubstituent ((S,S)/(R,S) = 89/11) also proceeded similarly in a high regioselectivity of >99:1.
29. 3-4 in 98% yield (GC purity = 99.9%; 99.7% ee).