Isomerization and deuterium scrambling evidence for a change in the rate-limiting step during imine hydrogenation by Shvo's hydroxycyclopentadienyl ruthenium hydride

Journal of the American Chemical Society

Volumn 127, Issue 6, 2005, Pages 1883-1894

  Casey, Charles P ^a   Johnson, Jeffrey B ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINES; HYDRIDES; HYDROGENATION; ISOTOPES; KETONES; ORGANOMETALLICS;

HYDROGEN TRANSFER; IMINES; INVERSE EQUILIBRIUM; KETONE REDUCTION;

ISOMERIZATION;

ALDEHYDE; AMINE; ANILINE DERIVATIVE; BUTYLAMINE; DEUTERIUM; HYDROGEN; HYDROXYCYCLOPENTADIENYL RUTHENIUM HYDRIDE; IMINE; KETONE; N BENZILIDENE TERT BUTYLAMINE; N BENZILIDENEPENTAFLUOROANILINE; N ISOPROPYL (4 METHYL) BENZILIDENE AMINE; RUTHENIUM COMPLEX; UNCLASSIFIED DRUG;

ARTICLE; HYDROGENATION; ISOMERIZATION; ISOTOPE ANALYSIS; PROTON TRANSPORT; ROOM TEMPERATURE;

ANILINE COMPOUNDS; CATALYSIS; CYCLOPENTANES; DEUTERIUM EXCHANGE MEASUREMENT; HYDROGENATION; IMINES; ISOMERISM; KINETICS; ORGANOMETALLIC COMPOUNDS; RUTHENIUM;

EID: 13644254490     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja044450t     Document Type: Article

References (24)

1. Noyori, R.; Hashiguchi, S. Acc. Chem. Res. 1997, 30, 97.
2. (b) Noyori, R.; Yamakawa, M.; Hashiguchi, S. J. Org. Chem. 2001, 66, 7931.
3. Noyori, R.; Ohkuma, T. Angew. Chem., Int. Ed. 2001, 40, 40.
4. Mashima, K.; Abe, T.; Tani, K. Chem. Lett. 1998, 1199.
5. (b) Mashima, K.; Abe, T.; Tani, K. Chem. Lett. 1998, 1201.
6. (c) Ito, M.; Hirakawa, M.; Murata, K.; Ikariya, T. Organometallics 2001, 20, 379.
7. Abdur-Rashid, K.; Clapham, S. E.; Hadzovic, A.; Harvey, J. N.; Lough, A. J.; Morris, R. H. J. Am. Chem. Soc. 2002, 124, 15104.
8. (b) Abdur-Rashid, K.; Faatz, M.; Lough, A. J.; Morris, R. H. J. Am. Chem. Soc. 2001, 123, 7473.
9. (c) Abdur-Rashid, K.; Lough, A. J.; Morris, R. H. Organometallics 2001, 20, 1047.
10. Mao, J.; Baker, D. C. Org. Lett. 1999, 1, 841.
11. Blum, Y.; Czarkie, D.; Rahamim, Y.; Shvo, Y. Organometallics 1985, 4, 1459.
12. (b) Shvo, Y.; Czarkie, D.; Rahamim, Y. J. Am. Chem. Soc. 1986, 108, 7400.
13. Casey, C. P.; Singer, S. W.; Powell, D. R.; Hayashi, R. K.; Kavana, M. J. Am. Chem. Soc. 2001, 123, 1090.
14. Casey, C. P.; Johnson, J. B. J. Org. Chem. 2003, 68, 1998.
15. Yamakawa, M.; Ito, H.; Noyori, R. J. Am. Chem. Soc. 2000, 122, 1466.
16. Samec, J. S. M.; Bäckvall, J.-E. Chem. - Eur. J. 2002, 8, 2955.
17. Uematsu, N.; Fujii, A.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1996, 118, 4916.
18. Subscripts of rate constants indicate the identity of the imine. The isotopomer of 5, when not 5-RuHOH, is also noted in the subscript.
19. 2O: Casey, C. P.; Johnson, J. B. Unpublished results.
20. Casey, C. P.; Bikzhanova, G. A. Unpublished results.
21. Casey, C. P.; Bikzhanova, G. A. Unpublished results.
22. Bushweller, C. H.; O'Neil, J. W.; Bilofsky, H. S. Tetrahedron 1972, 28 2697.
23. Upon the reduction of imine 10 with 5-RuDOH, the ratio of deuterium in the free imine and amine complex is 1:4, indicating that for dibenzylamine, complexation occurs competitively with dehydrogenation. Ignoring isotope effects, this indicates that ruthenium amine complex formation is favored by a factor of 2 over dehydrogenation.
24. Samec, J. S. M.; Éll, A. H.; Bäckvall, J.-E. Chem. Commun. Advance Article.