Thioether bond formation by SPASM domain radical SAM enzymes: Cα H-atom abstraction in subtilosin A biosynthesis

Chem Commun (Camb). 2016 May 7;52(37):6249-6252. doi: 10.1039/c6cc01317a. Epub 2016 Apr 18.

Abstract

AlbA is a radical SAM enzyme catalyzing the formation of three unusual thioether bonds in the antibiotic subtilosin A. We demonstrate here that AlbA catalyzes direct Cα H-atom abstraction and likely contains three essential [4Fe-4S] centers. This leads us to propose novel mechanistic perspectives for thioether bond catalysis by radical SAM enzymes.

MeSH terms

  • Anti-Bacterial Agents / biosynthesis*
  • Anti-Bacterial Agents / chemistry
  • Bacterial Proteins / chemistry
  • Bacterial Proteins / metabolism*
  • Bacteriocins / biosynthesis*
  • Bacteriocins / chemistry
  • Biocatalysis
  • Free Radicals / chemistry
  • Free Radicals / metabolism
  • Models, Molecular
  • Peptides, Cyclic / biosynthesis*
  • Peptides, Cyclic / chemistry
  • Sulfides / chemistry
  • Sulfides / metabolism*

Substances

  • Anti-Bacterial Agents
  • Bacterial Proteins
  • Bacteriocins
  • Free Radicals
  • Peptides, Cyclic
  • Sulfides
  • sboA protein, Bacillus subtilis