Structure-Guided Reprogramming of a Hydroxylase To Halogenate Its Small Molecule Substrate

Biochemistry. 2017 Jan 24;56(3):441-444. doi: 10.1021/acs.biochem.6b01173. Epub 2017 Jan 11.

Abstract

Enzymatic installation of chlorine/bromine into unactivated carbon centers provides a versatile, selective, and environmentally friendly alternative to chemical halogenation. Iron(II) and 2-(oxo)-glutarate (FeII/2OG)-dependent halogenases are powerful biocatalysts that are capable of cleaving aliphatic C-H bonds to introduce useful functional groups, including halogens. Using the structure of the Fe/2OG halogenase, WelO5, in complex with its small molecule substrate, we identified a similar N-acyl amino acid hydroxylase, SadA, and reprogrammed it to halogenate its substrate, thereby generating a new chiral haloalkyl center. The work highlights the potential of FeII/2OG enzymes as platforms for development of novel stereospecific catalysts for late-stage C-H functionalization.

MeSH terms

  • Bacterial Proteins / chemistry*
  • Bacterial Proteins / genetics
  • Bacterial Proteins / metabolism
  • Biocatalysis
  • Burkholderia / enzymology*
  • Burkholderia / genetics
  • Gene Expression
  • Green Chemistry Technology
  • Halogenation
  • Halogens / chemistry*
  • Halogens / metabolism
  • Iron / chemistry
  • Iron / metabolism
  • Ketoglutaric Acids / chemistry
  • Ketoglutaric Acids / metabolism
  • Mixed Function Oxygenases / chemistry*
  • Mixed Function Oxygenases / genetics
  • Mixed Function Oxygenases / metabolism
  • Oxidoreductases / chemistry*
  • Oxidoreductases / genetics
  • Oxidoreductases / metabolism
  • Protein Engineering*
  • Structural Homology, Protein
  • Substrate Specificity
  • Succinic Acid / chemistry
  • Succinic Acid / metabolism

Substances

  • Bacterial Proteins
  • Halogens
  • Ketoglutaric Acids
  • Succinic Acid
  • Iron
  • Mixed Function Oxygenases
  • Oxidoreductases