Skip to main content
SpringerLink
Log in

Mechanistic Investigation of the Gold-catalyzed Aerobic Oxidation of Alcohols

  • Published:
Catalysis Letters Aims and scope Submit manuscript

Abstract

The mechanism for the gold-catalyzed aerobic oxidation of alcohols was studied using a series of para-substituted benzyl alcohols (Hammett methodology). The competition experiments clearly show that the rate-determining step of the reaction involves the generation of a partial positive charge in the benzylic position (i.e. hydride abstraction). This was further substantiated by the determination of a significant kinetic isotope effect (kH/kD = 1.41), when employing an alcohol substrate deuterated in this position.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Scheme 1
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. (a) Hashmi ASK, Hutchings GJ (2006) Angew Chem Int Ed 45:7899–7936; (b) Edwards PP, Thomas JM (2007) Angew Chem 46:5480–5486

    Google Scholar 

  2. Hammer B, Nørskov JK (1995) Nature 376:238–240

    Article  CAS  Google Scholar 

  3. Haruta M, Kobayashi T, Sano H, Yamada N (1987) Chem Lett 16:405–408

    Article  Google Scholar 

  4. Hutchings GJ (1985) J Catal 96:292–295

    Article  CAS  Google Scholar 

  5. (a) Landon P, Collier PJ, Papworth AJ, Kiely CJ, Hutchings GJ (2002) Chem Commun 2058–2059; (b) Landon P, Collier PJ, Carley AF, Chatwick D, Papworth AJ, Burrows A, Kiely CJ, Hutchings GJ (2003) Phys Chem Chem Phys 5:1917–1923

  6. (a) Hashmi ASK (2004) Gold Bulletin 37(1–2):51–65; (b) Hashmi ASK (2005) Angew Chem Int Ed 44:6990–6993; (c) Hoffmann-Röder A, Krause N (2005) Org Biomol Chem 3:387–391

  7. (a) Taarning E, Nielsen IS, Egeblad K, Madsen R, Christensen CH (2007) Chem Sus Chem accepted; (b) Corma A, Iborra S, Velty A (2007) Chem Rev 107:2411–2502; (c) Haruta M (2007) Angew Chem Int Ed 46:7154

  8. Mallat T, Baiker A (2004) Chem Rev 104:3037–3058

    Article  CAS  Google Scholar 

  9. Janssens TVW, Clausen BS, Hvolbæk B, Falsig H, Christensen CH, Bligaard T, Nørskov JK (2007) Top Catal 44(1–2):15–26

    Article  CAS  Google Scholar 

  10. Christensen CH, Jørgensen B, Rass-Hansen J, Egeblad K, Madsen R, Klitgaard SK, Hansen SM, Hansen MR, Andersen HC, Riisager A (2006) Angew Chem Int Ed 45:4648–4651

    Article  CAS  Google Scholar 

  11. Biella S, Castiglioni GL, Fumagalli C, Prati L, Rossi M (2002) Catal Today 72:43–49

    Article  CAS  Google Scholar 

  12. (a) Bianchi C, Porta F, Prati L, Rossi M (2003) Top Catal 13:231–236; (b) Porta F, Prati L, Rossi M, Coluccia S, Martra G (2000) Catal Today 61:165–172; (c) Prati L, Porta F (2005) Appl Cat A 291:199–203

  13. (a) Comotti M, Della Pina C, Faletta E, Rossi M, Catal J (2006) 244:122–125; (b) Comotti M, Della Pina C, Falletta E, Rossi M (2006) Adv Synth Catal 348:313–316; (c) Comotti M, Della Pina C, Matarrese R, Rossi M (2004) Angew Chem Int Ed 43:5812–5815

    Google Scholar 

  14. Abad A, Almela C, Corma A, García H (2006) Chem Commun 3178–3180

  15. Nielsen IS, Taarning E, Egeblad K, Madsen R, Christensen CH (2007) Catal Lett 116:35–40

    Article  CAS  Google Scholar 

  16. (a) Hansch C, Leo A, Taft RW (1991) Chem Rev 91:165–195; (b) Hansch C, Gao H (1997) Chem Rev 97:2995–3059

  17. For other Hammett studies conducted using competition experiments, see: (a) Keinicke L, Fristrup P, Norrby P-O, Madsen R (2005) J Am Chem Soc 127:15756–15761; (b) Fristrup P, Le Quement S, Tanner D, Norrby P-O (2004) Organometallics 23:6160–6166

    Google Scholar 

  18. (a) Fristrup P, Dideriksen BB, Tanner D, Norrby P-O (2005) J Am Chem Soc 127:13672–13679; (b) Fristrup P, Jensen GH, Andersen MLN, Tanner D, Norrby P-O (2006) J Organomet Chem 2182–2198; (c) Fristrup P, Tanner D, Norrby P-O (2003) Chirality 15:360–368

  19. σ-values were obtained from ref. xvi

  20. Creary X, Mehrsheikh-Mohammadi ME, McDonald S (1987) J Org Chem 52:3254–3263

    Article  CAS  Google Scholar 

  21. Opre Z, Ferri D, Krumeich F, Mallat T, Baiker A (2006) J Catal 241:287–295

    Article  CAS  Google Scholar 

  22. Wesheimer FH (1961) Chem Rev 61:265

    Article  Google Scholar 

  23. Guzman J, Gates BC (2004) J Am Chem Soc 126:2672–2673

    Article  CAS  Google Scholar 

  24. Guzman J, Carretin S, Fierro-Gonzalez JC, Hao Y, Gates BC, Corma A (2005) Angew Chem Int Ed 44:4778–4781

    Article  CAS  Google Scholar 

  25. Enache DI, Edwards JK, Landon P, Solsona-Espriu B, Carley AF, Herzing AA, Watanabe M, Kiely CJ, Knight DW, Hutchings GJ (2006) Science 311:362–365

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Center for Sustainable and Green Chemistry is sponsored by the Danish National Research Foundation.

Author information

Authors and Affiliations

  1. Center for Sustainable and Green Chemistry, Technical University of Denmark, Kemitorvet, 2800, Lyngby, Denmark

    Peter Fristrup, Louise Bahn Johansen & Claus Hviid Christensen

Authors
  1. Peter Fristrup
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Louise Bahn Johansen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Claus Hviid Christensen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Claus Hviid Christensen.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Fristrup, P., Johansen, L.B. & Christensen, C.H. Mechanistic Investigation of the Gold-catalyzed Aerobic Oxidation of Alcohols. Catal Lett 120, 184–190 (2008). https://doi.org/10.1007/s10562-007-9301-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10562-007-9301-8

Keywords

Search

Navigation