Oxone-Mediated Oxidative Esterification of Heterocyclic Aldehydes Using Indium(III) Triflate


Recent investigations have shown the oxone-mediated oxidative methyl esterification of benzaldehyde derivatives using methanol. The reactions were accelerated in the presence of indium(III) triflate, a trivalent indium reagent, in many cases. Based on this method of methyl esterification of benzaldehyde derivatives, we further explored an application to heterocyclic aldehydes. The reactions were examined using methanol as well as other alcohols in order to establish a suitable range.

Share and Cite:

T. Mineno, S. Yoshino and A. Ubukata, "Oxone-Mediated Oxidative Esterification of Heterocyclic Aldehydes Using Indium(III) Triflate," Green and Sustainable Chemistry, Vol. 4 No. 1, 2014, pp. 20-23. doi: 10.4236/gsc.2014.41004.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] N. Yamamoto, Y. Obora and Y. Ishii, “Iridium-Catalyzed Oxidative Methyl Esterification of Primary Alcohols and Diols with Methanol,” Journal of Organic Chemistry, Vol. 76, No. 8, 2011, pp. 2937-2941.
[2] S. Kiyooka, Y. Wada, M. Ueno, T. Yokoyama and R. Yokoyama, “[IrCl(cod)]2-Catalyzed Direct Oxidative Esterification of Aldehydes with Alcohols,” Tetrahedron, Vol. 63, No. 51, 2007, pp. 12695-12701.
[3] S. Kiyooka, M. Ueno and E. Ishii, “Iridium-Catalyzed Oxidative Esterification Reaction of Aliphatic Aldehydes and Olefinic Alcohols with Pre-Coordination of the Double Bond of Alcohols to Iiridium,” Tetrahedron Letters, Vol. 46, No. 27, 2005, pp. 4639-4642.
[4] J. H. Espenson, Z. Zhu and T. H. Zauche, “Bromide Ions and Methyltrioxorhenium as Cocatalysts for Hydrogen Peroxide Oxidations and Brominations,” Journal of Organic Chemistry, Vol. 64, No. 4, 1999, pp. 1191-1196.
[5] S. Murahashi, T. Naota, K. Ito, Y. Maeda and H. Taki, “Ruthenium-Catalyzed Oxidative Transformation of Alcohols and Aldehydes to Esters and Lactones,” Journal of Organic Chemistry, Vol. 52, No. 19, 1987, pp. 4319-4327.
[6] R. Grigg, T. R. B. Mitchell and S. Sutthivaiyakit, “Oxidation of Alcohols by Transition Metal Complexes. IV. The Rhodium-Catalyzed Synthesis of Esters from Aldehydes and Alcohols,” Tetrahedron, Vol. 37, No. 24, 1981, pp. 4313-4319.
[7] R. Lerebours and C. Wolf, “Chemoselective Nucleophilic Arylation and Single-Step Oxidative Esterification of Aldehydes Using Siloxanes and a Palladium-Phosphinous Acid as a Reaction Switch,” Journal of the American Chemical Society, Vol. 128, No. 40, 2006, pp. 13052-13053.
[8] L.-L. Wei, L.-M. Wei, W.-B. Pan and M.-J. Wu, “Palladium-Catalyzed Esterification-Hydroarylation Reactions of 2-Alkynylbenzaldehydes with Aryl Iodides in Methanol,” Synlett, No. 9, 2004, pp. 1497-1502.
[9] R. K. Sharma and C. Sharma, “Efficient Oxidative Methyl Esterification of Aldehydes by Silica-Supported Manganese Complex: Clean and Recyclable Catalyst,” Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, Vol. 48, No. 2, 2011, pp. 155-163.
[10] R. S. Reddy, J. N. Rosa, L. F. Veiros, S. Caddick and P. M. P. Gois, “NHC/Iron Cooperative Catalysis: Aerobic Oxidative Esterification of Aldehydes with Phenols,” Organic & Biomolecular Chemistry, Vol. 9, No. 9, 2011, pp. 3126-3129. http://dx.doi.org/10.1039/c1ob05151b
[11] W.-J. Yoo and C.-J. Li, “Copper-Catalyzed Oxidative Esterification of Alcohols with Aldehydes Activated by Lewis Acids,” Tetrahedron Letters, Vol. 48, No. 6, 2007, pp. 1033-1035.
[12] G. Qian, R. Zhao, D. Ji, G. Lu, Y. Qi and J. Suo, “Facile Oxidation of Aldehydes to Esters Using S SnO2/SBA-1-H2O2,” Chemistry Letters, Vol. 33, No. 7, 2004, pp. 834-835. http://dx.doi.org/10.1246/cl.2004.834
[13] P. J. Garegg, L. Olsson and S. Oscarson, “Synthesis of Methyl (Ethyl 2-O-acyl-3,4-di-O-benzyl-1-thio-β-D- glucopyranosid)uronates and Evaluation of Their Use as Reactive β-Selective Glucuronic Acid Donors,” Journal of Organic Chemistry, Vol. 60, No. 7, 1995, pp. 2200-2204.
[14] B. O’Connor and G. Just, “A New Method for the Conversion of Aldehydes to Methyl Esters Using Pyridinium Dichromate and Methanol in Dimethylformamide,” Tetrahedron Letters, Vol. 28, No. 28, 1987, pp. 3235-3236.
[15] S. P. Chavan, S. W. Dantale, C. A. Govande, M. S. Venkatraman and C. Praveen, “Titanosilicate (TS-1) Catalyzed Oxidation of Aromatic Aldehydes to Esters,” Synlett, No. 2, 2002, pp. 267-268.
[16] R. Gopinath and B. K. Patel, “A Catalytic Oxidative Esterification of Aldehydes Using V2O5-H2O2,” Organic Letters, Vol. 2, No. 5, 2000, pp. 577-579.
[17] R. Gopinath, B. Barkakaty, B. Talukdar and B. K. Patel, “Peroxovanadium-Catalyzed Oxidative Esterification of Aldehydes,” Journal of Organic Chemistry, Vol. 68, No. 7, 2003, pp. 2944-2947.
[18] X.-F. Wu and C. Darcel, “Iron-Catalyzed One-Pot Oxidative Esterification of Aldehydes,” European Journal of Organic Chemistry, Vol. 2009, No. 8, 2009, pp. 1144-1147.
[19] X.-F. Wu, “Zinc-Catalyzed Oxidative Esterification of Aromatic Aldehydes,” Tetrahedron Letters, Vol. 53, No. 26, 2012, pp. 3397-3399.
[20] T. Mineno and H. Kansui, “High Yielding Methyl Esterification Catalyzed by Indium(III) Chloride,” Chemical & Pharmaceutical Bulletin, Vol. 54, No. 6, 2006, pp. 918-919. http://dx.doi.org/10.1248/cpb.54.918
[21] T. Mineno and M. J. Miller, “Stereoselective Total Synthesis of Racemic BCX-1812 (RWJ-270201) for the Development of Neuraminidase Inhibitors as Anti-Influenza Agents,” Journal of Organic Chemistry, Vol. 68, No. 17, 2003, pp. 6591-6596.
[22] T. Mineno, “A Fast and Practical Approach to Tetrahydropyranylation and Depyranylation of Alcohols Using Indium Triflate,” Tetrahedron Letters, Vol. 43, No. 44, 2002, pp. 7975-7978.
[23] T. Mineno, N. Nikaido and H. Kansui, “One-Step Transformation of Tetrahydropyranyl Ethers Using Indium(III) Triflate as the Catalyst,” Chemical & Pharmaceutical Bulletin, Vol. 57, No. 10, 2009, pp. 1167-1170.
[24] T. Mineno, M. Sakai, A. Ubukata, K. Nakahara, H. Yoshimitsu and H. Kansui, “The Effect of Indium Triflate(III) in Oxone-Mediated Oxidative Methyl Esterification of Aldehydes,” Chemical & Pharmaceutical Bulletin, Vol. 61, No. 8, 2013, pp. 870-887.
[25] B. R. Travis, M. Silvakumar, G. O. Hollist and B. Borhan, “Facile Oxidation of Aldehydes to Acids and Esters with Oxone,” Organic Letters, Vol. 5, No. 7, 2003, pp. 1031-1034. http://dx.doi.org/10.1021/ol0340078

Copyright © 2023 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.