SiliaCat TEMPO: An effective and useful oxidizing catalyst

Organic Process Research and Development

Volumn 11, Issue 4, 2007, Pages 766-768

  Michaud, Annie ^a   Gingras, Geneviève ^a   Morin, Michel ^a   Béland, François ^a   Ciriminna, Rosaria ^b   Avnir, David ^c   Pagliaro, Mario ^b  

^a SiliCyde Inc   (Canada)

^b CNR   (Italy)

^c HEBREW UNIVERSITY OF JERUSALEM   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 34547881872     PISSN: 10836160     EISSN: None     Source Type: Journal    
DOI: 10.1021/op700050j     Document Type: Article

References (21)

1. de Nooy, A. E. J.; van Bekkum, H.; Besemer, A. Synthesis 1996, 1153.
2. Alternatively, in conjunction with ruthenium and copper they catalyze aerobic oxidations of alcohols where the role of TEMPO is to facilitate regeneration of the active catalyst (Ru and Cu). For a recent discussion on the topic, see: Sheldon, R. A.; Arends, I. W. C. E. Adv. Synth. Catal. 2004, 346, 1051.
3. 2 developed by Semmelack in the early 1980s to synthesize retinal from retinol, and Wacker Chemie uses continuous oxidation with bleach as the primary oxidant to synthesize aldehydes with additional substituents in the δ or γ position.
4. Fritz-Langhals, E. Org. Process Res. Dev. 2005, 9, 577.
5. For this technology, the pharmaceutical manufacturer Pharmacia&Upjohn was awarded the 1996 Presidential Green Chemistry Challenge Award. See at: http://epa.gov/greenchemistry/pubs/docs/ award_entries_and_recipients1996.pdf.
6. Personal information (to M.P) from ChemConserve Ltd.
7. Approaches include heterogenization over organic and inorganic polymeric supports. An overview is given in ref 2.
8. Zaragoza Dörwald, F. Organic Synthesis on Solid Phase; Wiley-VCH: Weinheim, 2002.
9. For instance, by the United States chemicals supplier Aldrich which commercializes TEMPO supported over both polymeric organic resin and silica gel.
10. Solid oxidation catalysts are indeed "philosophers' stones": Sheldon, R. A.; Wallau, M.; Arends, I. W. C. E.; Schuchardt, U. Ace Chem. Res. 1998, 31, 485.
11. Pagliaro, M.; Avnir, D.; Blum, J.; Deganello, G. (SiliCycle Inc.). U.S. Patent 6,797,773 B1, 2004.
12. Ciriminna, R.; Bolm, C.; Fey, T.; Pagliaro, M. Adv. Synth. Catal. 2002, 344, 159.
13. Gancitano, P.; Ciriminna, R.; Testa, M. L.; Fidalgo, A.; Ilharco, L. M.; Pagliaro, M. Org. Biomol. Chem. 2005, 3, 389.
14. Testa, M. L.; Ciriminna, R.; Hajji, C.; Zaballos Garcia, E.; Ciclosi, M.; Sepulveda Arques, J.; Pagliaro, M. Adv. Synth. Catal. 2004, 346, 655.
15. Fidalgo, A.; Ciriminna, R.; Ilharco, L. M.; Pagliaro, M. Chem. Mater. 2005, 17, 6686.
16. Chlorinated solvent DCM of course is far from being a "green" solvent, and the reason for employing DCM here is due to customer requirements. SiliaCat TEMPO performs equally well in aliphatic solvents as described in the case of another heterogenized TEMPO catalyst: Dijksman, A.; Arends, I. W. C E.; Sheldon, R. A. Chem. Commun. 2000, 271.
17. Palmisano, G.; Ciriminna, R.; Pagliaro, M. Adv. Synth. Catal. 2006, 348, 2033.
18. Fey, T.; Fischer, H.; Bachmann, S.; Albert, K.; Bolm, C. J. Org. Chem. 2001, 66, 8154.
19. Pagliaro, M.; Ciriminna, R.; Wong Chi Man, M.; Campestrini, S. J. Phys. Chem. B 2006, 110, 1976.
20. Pagliaro, M.; Ciriminna, R.; Palmisano, G. Chem. Soc. Rev. Published online http://dx.doi.org/ 10.1039/b611171h.
21. Reetz, M. T.; Tielmann, P.; Wiesenhöfer, W.; Konen, W.; Zonta, A. Adv. Synth. Catal. 2003, 345, 717.