Theoretical insights into heme-catalyzed oxidation of cyclohexane to adipic acid

Inorg Chem. 2011 Feb 21;50(4):1194-202. doi: 10.1021/ic101405u. Epub 2011 Jan 26.

Abstract

Adipic acid is a key compound in the chemical industry, where it is mainly used in the production of polymers. The conventional process of its generation requires vast amounts of energy and, moreover, produces environmentally deleterious substances. Thus, there is interest in alternative ways to gain adequate amounts of adipic acid. Experimental reports on a one-pot iron-catalyzed conversion of cyclohexane to adipic acid motivated a theoretical investigation based on density functional theory calculations. The process investigated is interesting because it requires less energy than contemporary methods and does not produce environmentally harmful side products. The aim of the present contribution is to gain insight into the mechanism of the iron-catalyzed cyclohexane conversion to provide a basis for the further development of this process. The rate-limiting step of the process is discussed, but considering the accuracy of the calculations, it is difficult to ensure whether the rate-limiting step is in the substrate oxidation or in the generation of the catalytically active species. It is shown that the slowest step in the substrate oxidation is the conversion of cyclohexanol to cyclohexane-1,2-diol. Hydrogen-atom transfer from one of the OH groups of cyclohexane-1,2-diol makes the intradiol cleavage occur spontaneously.

MeSH terms

  • Adipates / chemical synthesis*
  • Adipates / chemistry
  • Algorithms
  • Catalysis
  • Cyclohexanes / chemistry*
  • Heme / chemistry*
  • Hydrogen / chemistry
  • Iron / chemistry
  • Kinetics
  • Models, Chemical*
  • Oxidation-Reduction
  • Quantum Theory
  • Thermodynamics

Substances

  • Adipates
  • Cyclohexanes
  • Heme
  • Cyclohexane
  • adipic acid
  • Hydrogen
  • Iron