An evaluation of the Noyori system "in reverse": Thermodynamic and kinetic parameters of secondary alcohol transfer dehydrogenation catalyzed by [(η6-1-iPr-4-Me-C6H4)Ru(HN-CR′R″-CR′R″NTs)], R′ = H, Me; Ph, R″ = H, Me

Journal of Molecular Catalysis A: Chemical

Volumn 290, Issue 1-2, 2008, Pages 1-14

  Bierenstiel, Matthias ^a   Dymarska, Magdalena ^a   de Jong, Ebbing ^a   Schlaf, Marcel ^a  

^a UNIVERSITY OF WATERLOO   (Canada)

Author keywords

Alcohol oxidation; Catalysis; Ruthenium complexes; Transfer hydrogenation

Indexed keywords

COMPUTER NETWORKS; RUTHENIUM;

KINETIC (POLYM.); RUTHENIUM (IV) COMPLEXES; SECONDARY ALCOHOLS; TRANSFER DEHYDROGENATION;

RUTHENIUM COMPOUNDS;

EID: 46149099775     PISSN: 13811169     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.molcata.2008.05.009     Document Type: Article

References (28)

1. Smith M. March's Advanced Organic Chemistry: Reactions, Mechanism and Structure. sixth ed. (2007), John Wiley & Sons, New York
2. Larock R.C. Comprehensive Organic Transformations: A Guide to Functional Group Preparations. second ed. (1999), Wiley-VCH, New York
3. Sakaguchi S., Kikuchi D., and Ishii Y. Bull. Chem. Soc. Jpn. 70 (1997) 2561-2566
4. Bierenstiel M., D'Hondt P.J., and Schlaf M. Tetrahedron 61 (2005) 4911-4917
5. Isaac I., Aizel G., Stasik I., Wadouachi A., and Beaupere D. Synlett (1998) 475-476
6. Freimund S., Huwig A., Giffhorn F., and Köpper S. Chem. Eur. J. 4 (1998) 2442-2455
7. Liu H.-M., Sato Y., and Tsuda Y. Chem. Pharm. Bull. 41 (1993) 491-501
8. Haack K.-J., Hashiguchi S., Fujii A., Ikariya T., and Noyori R. Angew. Chem. Int. Ed. Engl. 36 (1997) 285-288
9. Noyori R., and Hashigushi S. Acc. Chem. Res. 30 (1997) 97-102
10. Yamakawa M., Ito H., and Noyori R. J. Am. Chem. Soc. 122 (2000) 1466-1478
11. Noyori R., Yamakawa M., and Hashiguchi S. J. Org. Chem. 66 (2001) 7931-7944
12. Noyori R. Angew. Chem. Int. Ed. 41 (2002) 2008-2022
13. Hashiguchi S., Fujii A., Haack K.-J., Matsumura K., Ikariya T., and Noyori R. Angew. Chem. Int. Ed. Engl. 36 (1997) 288-290
14. Barros M.T., and Siñeriz F. Tetrahedron 56 (2000) 4759-4764
15. Cheng H.-Y., Cheng P.-H., Lee C.-F., and Peng S.-M. Inorg. Chim. Acta 181 (1991) 145-147
16. Sayre R. J. Am. Chem. Soc. 77 (1955) 6689-6690
17. Hayes A., Clarkson G., and Wills M. Tetrahedron: Asymmetry 15 (2004) 2079-2084
18. Takehara J., Hashiguchi S., Fujii A., Inoue S., Ikariya T., and Noyori R. J. Chem. Soc., Chem. Commun. (1996) 233-234
19. Bach R.D., and Dmitrenko O. J. Am. Chem. Soc. 128 (2006) 4598-4611
20. Lozinskaya N.A., Tkachenko S.E., and Zefirov N.S. Russ. J. Org. Chem. 38 (2002) 1149-1153
21. Bennett M.A., Huang T.-N., Matheson T.W., and Smith A.K. In: Fackler J.P. (Ed). Inorganic Synthesis (1982), John Wiley & Sons, New York 74-77
22. Repeated attempts to obtain conventional elemental analysis failed due to the air-sensitive nature of the complexes.
23. Huang Y.-H., and Gladysz J.A. J. Chem. Ed. 65 (1988) 298-303
24. Delbecq F., and Sautet P. J. Am. Chem. Soc. 114 (1992) 2446-2455
25. Details of the calculation parameters as well as the numerical results are given in the Supplementary Material.
26. NMR spectroscopy would be a logical choice here. However in our experience overlapping signals even at fields >400 MHz make the required accurate quantitation by integration effectively impossible.
27. By using equal concentration for all reactants including solvents, the reaction is set-up in neutral. Thus depending on its ΔG° value the reaction itself determines if it "wants" to proceed into an oxidizing or reducing direction.
28. Detailed descriptions of and data obtained from these experiments for all ketone/alcohol pairs are contained in the Supplementary Material.