Asymmetric hydrogenation of protected allylic amines

Organic Letters

Volumn 12, Issue 18, 2010, Pages 4201-4203

  Steinhuebel, Dietrich P ^a,b   Krska, Shane W ^a,b   Alorati, Anthony ^a,b   Baxter, Jenny M ^a,b   Belyk, Kevin ^a,b   Bishop, Brian ^a,b   Palucki, Michael ^a,b   Sun, Yongkui ^a,b   Davies, Ian W ^a,b  

^a MERCK RESEARCH LABORATORIES   (United States)

^b Merck Sharp & Dohme Limited   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; AMINE; AZEPINE DERIVATIVE; CAPROLACTAM; IMIDAZOLE DERIVATIVE; N (6 (2,3 DIFLUOROPHENYL) 2 OXO 1 (2,2,2 TRIFLUOROETHYL)AZEPAN 3 YL) 4 (2 OXO 2,3 DIHYDRO 1H IMIDAZO(4,5 B)PYRIDIN 1 YL)PIPERIDINE 1 CARBOXAMIDE; N-(6-(2,3-DIFLUOROPHENYL)-2-OXO-1-(2,2,2-TRIFLUOROETHYL)AZEPAN-3-YL)-4-(2-OXO-2,3-DIHYDRO-1H-IMIDAZO(4,5-B)PYRIDIN-1-YL)PIPERIDINE-1-CARBOXAMIDE;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; HYDROGENATION; STEREOISOMERISM; SYNTHESIS;

ALLYL COMPOUNDS; AMINES; AZEPINES; CAPROLACTAM; CATALYSIS; HYDROGENATION; IMIDAZOLES; MOLECULAR STRUCTURE; STEREOISOMERISM;

EID: 77956591000     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol101804e     Document Type: Article

References (32)

1. Paone, D. V.; Shaw, A. W.; Nguyen, D. N.; Burgey, C. S.; Deng, Z. J.; Kane, S. A.; Koblan, K. S.; Salvatore, C. A.; Hershey, J. C.; Wong, B.; Roller, S. G.; Miller-stein, C.; Graham, S. L.; Vacca, J. P.; Williams, T. M. J. Med. Chem. 2007, 50, 5564-5567
2. For the first synthesis, see
3. Burgey, C. S.; Paone, D. V.; Shaw, A. W.; Deng, J. Z.; Nguyen, D. N.; Potteiger, C. M.; Graham, S. L.; Vacca, J. P.; Williams, T. M. Org. Lett. 2008, 10, 3235-3238
4. For an alternate approach, see: Janey, J. M.; Orella, C. J.; Njolito, E.; Baxter, J. M.; Rosen, J. D.; Palucki, M.; Sidler, R. R.; Li, W. L.; Kowal, J. J.; Davies, I. W. J. Org. Chem. 2008, 73, 3212-3217
5. Shultz, S. C.; Krska, S. K. Acc. Chem. Res. 2007, 12, 1320-1326
6. Wang, C.-J.; Sun, X.; Zhang, X. Angew. Chem., Int. Ed. 2005, 44, 4933-4935
7. Deng, J.; Duan, Z.-C.; Huang, J.-D.; Hu, X.-P.; Wang, D.-Y.; Yu, S.-B.; Xu, X.-F.; Zheng, Z. Org. Lett. 2007, 9, 4825-4828
8. Yamano, T.; Yamashita, M.; Adachi, M.; Tanaka, M.; Matsumoto, K.; Kawada, M.; Uchikawa, O.; Fukatsu, K.; Ohkawa, S. Tetrahedron: Asymmetry 2006, 17, 184-190
9. Fahrang, R.; Sinou, D. Bull. Soc. Chim. Belg. 1989, 98, 387-393
10. Saylik, D.; Campi, E. M.; Donohue, A. C.; Jackson, W. R.; Robinson, A. J. Tetrahedron: Asymmetry 2001, 12, 657-667
11. Sun, X.; Zhou, L.; Li, W.; Zhang, X. J. Org. Chem. 2007, 72, 1002-1005
12. Limanto, J.; Shultz, C. S.; Dorner, B.; Desmond, R. A.; Devine, P. N.; Krska, S. W. J. Org. Chem. 2008, 73, 1639-1642
13. Brown, J. M.; Parker, D. J. Org. Chem. 1982, 47, 2722-2725
14. Broene, R. D.; Buchwald, S. L. J. Am. Chem. Soc. 1993, 115, 12569-12570
15. Yamashita, M.; Yamano, T. Chem. Lett. 2009, 38, 100-101
16. Burk, M. A.; Allen, J. G.; Kiesman, W. F. J. Am. Chem. Soc. 1998, 120, 657-663
17. For unsaturated ester preparation, see
18. Baxter, J. M.; Steinhuebel, D. P.; Palucki, M.; Davies, I. W. Org. Lett. 2005, 7, 215-218
19. Genet, J.-P. Acc. Chem. Res. 2003, 36, 908-918 and references therein
20. Dobbs, D. A.; Vanhessche, K. P. M.; Brazi, E.; Rautenstrauch, V.; Lenoir, J.-V.; Genet, J.-P.; Wiles, J.; Bergens, S. H. Angew. Chem., Int. Ed. 2000, 39, 11, 1992-1995
21. Tang, W.; Wu, S.; Zhang, X. J. Am. Chem. Soc. 2003, 125, 9570
22. Benincori, T.; Cesarotti, E.; Piccolo, O.; Sannicol, F. J. Org. Chem. 2000, 65, 2043-2047
23. 4/(-)-TMBTP to afford 4 with identical enantioselectivity at the benzylic center.
24. The monoreduced bis-Boc derivative was used. For similar results see
25. Cui, X.; Burgess, K. Chem. Rev. 2005, 105, 3272-3296
26. See Supporting Information for experimental details.
27. A 96:4 ratio of trans: cis diastereomers was obtained after heating at 55 °C. For use of salicylaldehyde derivatives in epimerization, see
28. Reider, P. J.; Davis, P.; Hughes, D. L.; Grabowski, E. J. J. J. Org. Chem. 1987, 52, 955-957
29. Armstrong, J. D.; Eng, K. K.; Keller, J. L.; Purick, R. M.; Hartner, F. W.; Choi, W. B.; Askin, D.; Volante, R. P. Tetrahedron Lett. 1994, 35, 3239-3242
30. Although the N-Boc analogue of 14 also performs in the reaction, the acetamide-protected gives higher reactivity and selectivity.
31. The olefin geometry was confirmed by NOE studies.
32. Under these conditions the enantiomeric ratio decreases from 96:4 to 83:17, consistent with a kinetic isotope effect favoring olefin isomerization over catalyst turnover via reductive elimination.