Abstract
The hydrothermal experiments with ketones and formic acid showed that the hydrogen transfer reduction of ketones can be conducted using formic acid as a hydride donor in the presence of NaOH at 300 °C. The yield of alcohols was considerably higher at a much lower ratio of hydrogen source to ketones than the traditional Meerwein-Ponndorf-Verley (MPV) reduction, reaching 60% for isopropanol from acetone and 70% for lactic acid from pyruvic acid. Water molecules may act as a catalyst in the hydrogen transfer reduction of ketones under hydrothermal conditions.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Akiya, N., Savage, P.E., 2002. The roles of water for chemical reactions in high-temperature water. Chemical Reviews, 102(8):2725–2750. [doi:10.1021/cr000668w]
Alonso, F., Riente, P., Yus, M., 2008a. Hydrogen-transfer reduction of carbonyl compounds catalysed by nickel nanoparticles. Tetrahedron Letters, 49(12):1939–1942. [doi:10.1016/j.tetlet.2008.01.097]
Alonso, F., Riente, P., Yus, M., 2008b. Hydrogen-transfer reduction of carbonyl compounds promoted by nickel nanoparticles. Tetrahedron, 64(8):1847–1852. [doi:10.1016/j.tet.2007.11.093]
Campbell, E.J., Zhou, H., Nguyen, S.T., 2001. Catalytic Meerwein-Ponndorf-Verley reduction by simple aluminum complexes. Organic Letters, 3(15):2391–2393. [doi:10.1021/ol0162116]
Creyghton, E.J., Ganeshie, S.D., Downing, R.S., van Bekkum, H., 1997. Stereoselective Meerwein-Ponndorf-Verley and oppenauer reactions catalysed by zeolite BEA. Journal of Molecular Catalysis A: Chemical, 115(3):457–472. [doi:10.1016/S1381-1169(96)00351-2]
de Graauw, C.F., Peters, J.A., van Bekkum, H., Huskens, J., 1994. Meerwein-Ponndorf-Verley reductions and oppenauer oxidations: an integrated approach. Synthesis, 1994(10):1007–1017. [doi:10.1055/s-1994-25625]
Ekström, J., Wettergren, J., Adolfsson, H., 2007. A simple and efficient catalytic method for the reduction of ketones. Advanced Synthesis & Catalysis, 349(10):1609–1613. [doi:10.1002/adsc.200700091]
Fujii, A., Hashiguchi, S., Uematsu, N., Ikariya, T., Noyori, R., 1996. Ruthenium(II)-catalyzed asymmetric transfer hydrogenation of ketones using a formic acid-triethylamine mixture. Journal of the American Chemical Society, 118(10):2521–2522.
Jin, F.M., Kishita, A., Moriya, T., Enomoto, H., 2001. Kinetics of oxidation of food wastes with H2O2 in supercritical water. The Journal of Supercritical Fluids, 19(3):251–262. [doi:10.1016/S0896-8446(00)00094-2]
Jin, F.M., Zhou, Z., Enomoto, H., Moriya, T., Higashijima, H., 2004. Conversion mechanism of cellulosic biomass to lactic acid in subcritical water and acid-base catalytic effect of subcritical water. Chemistry Letters, 33(2):126–127. [doi:10.1246/cl.2004.126]
Jin, F.M., Yun, J., Li, G.M., Kishita, A., Tohji, K., Enomoto, H., 2008. Hydrothermal conversion of carbohydrate biomass into formic acid at mild temperatures. Green Chemistry, 10(6):612–615. [doi:10.1039/b802076k]
Kuhlmann, B., Arnett, E.M., Siskin, M., 1994. Classical or ganic reactions in pure superheated water. The Journal of Organic Chemistry, 59(11):3098–3101. [doi:10.1021/jo00090a030]
Larock, R.C., 1989. Comprehensive Organic Transformation. VCH Publication, New York, p.35–39.
Li, C., Yamai, I., Murase, Y., Kato, E., 1989. Formation of acicular monoclinic zirconia particles under hydrothermal conditions. Journal of the American Ceramic Society, 72(8):1479–1482. [doi:10.1111/j.1151-2916.1989.tb07681.x]
Matharu, D.S., Morris, D.J., Clarkson, G.J., Wills, M., 2006. An outstanding catalyst for asymmetric transfer hydrogenation in aqueous solution and formic acid/triethylamine. Chemical Communications, 30:3232–3234. [doi:10.1039/b606288a]
Meerwein, H., Schmidt, R., 1925. Ein neues verfahren zur reaktion von aldehyden und ketonen. Justus Liebigs Annalen der Chemie, 444(1):221–238 (in German).
Naskar, S., Bhattacharjee, M., 2007. Regiospecific solvent-free transfer hydrogenation of α, β-unsaturated carbonyl compounds catalyzed by a cationic ruthenium(II) compound. Tetrahedron Letters, 48(3):465–467. [doi:10.1016/j.tetlet.2006.11.063]
Ponndorf, W., 1926. Der reversible austausch der oxydationsstufen zwischen aldehyden oder ketonen einerseits und primären oder sekundären alkoholen anderseits. Zeitschrift für Angewandte Chemie, 39(5):138–143 (in Germany). [doi:10.1002/ange.19260390504]
Ruiz, J.R., Jiménez-Sanchidriána, C., Hidalgoa, J.M., 2007. Meerwein-Ponndorf-Verley reaction of acetophenones with 2-propanol over MgAl mixed oxide: the substituent effect. Catalysis Communications, 8(7):1036–1040. [doi:10.1016/j.catcom.2006.10.007]
Shaw, R.W., Brill, Y.B., Clifford, A.A., Eckert, C.A., Franck, E.U., 1991. Supercritical water a medium for chemistry. Chemical Engineering News, 69(51):26–39.
Sheldon, R.A., 1994. Consider the environmental quotient. ChemTech, 24(3):38–47.
Tsujino, Y., Wakai, C., Matubayasi, N., Nakahara, M., 1999. Noncatalytic cannizzaro-type reaction of formaldehyde in hot water. Chemistry Letters, 28(4):287–288. [doi:10.1246/cl.1999.287]
Watanabe, M., Sato, T., Inomata, H., Smith, R.L., Arai, K., Kruse, A., Dinjus, E., 2004. Chemical reactions of C1 compounds in near-critical and supercritical water. Chemical Reviews, 104(12):5803–5822. [doi:10.1021/cr020415y]
Author information
Authors and Affiliations
Corresponding author
Additional information
Project supported by the State Key Laboratory of Pollution Control and Resources Reuse in China (Tongji University) (No. PCRRK08002), the National Key Technology R&D Program of China (No. 2008BAJ08B13), and the Shanghai Pujiang Elitist Program of China (No. 07pj14083)
Rights and permissions
About this article
Cite this article
Shen, Z., Jin, Fm., Zhang, Yl. et al. Hydrogen transfer reduction of ketones using formic acid as a hydrogen donor under hydrothermal conditions. J. Zhejiang Univ. Sci. A 10, 1631–1635 (2009). https://doi.org/10.1631/jzus.A0920097
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1631/jzus.A0920097