Project Details

Stanley and coworkers reported the catalytic transformation of aldehydes and water to carboxylic acids and hydrogen as a side reaction observed during rhodium-catalyzed hydroformylation, and named this reaction the “aldehyde-water shift (AWS)”. ¹ If a practical catalyst for this reaction could be developed, there would be a number of potential applications, including transformation of HMF into furan dicarboxylic acid (FDCA), which could be used as a monomer in polyesters produced from renewable sources, and the utilization of isobutanal (the branched isomer resulting from hydroformylation of propylene) to make isobutyric acid, which can be used to make methacrylate esters for polymers. Our goals are to develop both homogeneous and heterogeneous systems capable of catalyzing this reaction.

Reference ¹: Stanley, G. G.; Aubry, D. A.; Bridges, N.; Barker, B.; Courtney, B. Prepr. Pap. Am. Chem. Soc., Div. Fuel Chem. 2004, 49, 712.

The Aldehyde-Water Shift Reaction

Recent Publications and Patents

  • Ou, W. C.; Cundari, T. R. "DFT Modeling of the Aldehyde-Water Shift Reaction with a Cationic Cp*Ir Catalyst", ACS Catal., 2015, 5, 225-232. (DOI: 10.1021/cs501222m)
  • Cheng, C.; Kim, B. G.; Guironnet, D.; Brookhart, M.; Guan, C.; Wang, D. Y.; Krogh-Jespersen, K.; Goldman, A. S. "Synthesis and Characterization of Carbazolide-based Iridium PNP Pincer Complexes. Mechanistic and Computational Investigation of Alkene Hydrogenation: Evidence for an IrIII/Ir(V)/IrIII Catalytic Cycle", J. Am. Chem. Soc., 2014, 136, 6672-6683. (DOI: 10.1021/ja501572g)
  • Kumar, A.; Mironov, O.; Saxon, R.; Goldman, A. "Alkane Dehydrogenation Process", International Patent Application filed March, 2014.