An ab initio study of electronic factors in metabolic hydroxylation of aliphatic carbon atoms

J Med Chem. 1978 Jul;21(7):683-6. doi: 10.1021/jm00205a017.


The monooxygenase-mediated hydroxylations of aliphatic carbon atoms are known to be regioselective for positions alpha to heteroatoms or to pi systems (aromatic rings, carbon-carbon double bonds, carbonyl groups). Ab initio calculations (STO-3G and in some cases 4-31G) were performed on model molecules, indicating that the Mulliken overlap populations (taken as indices of electron bond densities) of Calpha-H bonds being regioselectively hydroxylated are larger than Cbeta-H and Cgamma-H overlap populations. These results support the hypothesis that metabolic C-hydroxylations occur by insertion of an activated oxygen species of electrophilic nature, probably oxene.

MeSH terms

  • Carbon / metabolism*
  • Chemical Phenomena
  • Chemistry, Physical
  • Electrons
  • Hydroxylation
  • Quantum Theory
  • Structure-Activity Relationship


  • Carbon