Late-Stage Chemoenzymatic Installation of Hydroxy-Bearing Allyl Moiety on the Indole Ring of Tryptophan-Containing Peptides

Chemistry. 2022 Apr 6;28(20):e202104614. doi: 10.1002/chem.202104614. Epub 2022 Mar 10.


The late-stage functionalization of indole- and tryptophan-containing compounds with reactive moieties facilitates downstream diversification and leads to changes in their biological properties. Here, the synthesis of two hydroxy-bearing allyl pyrophosphates is described. A chemoenzymatic method is demonstrated which uses a promiscuous indole prenyltransferase enzyme to install a dual reactive hydroxy-bearing allyl moiety directly on the indole ring of tryptophan-containing peptides. This is the first report of late-stage indole modifications with this reactive group.

Keywords: C−H activation; allylation; biocatalysis; functionalization; indole prenyltransferase.

MeSH terms

  • Dimethylallyltranstransferase*
  • Indoles / chemistry
  • Peptides / chemistry
  • Tryptophan* / chemistry


  • Indoles
  • Peptides
  • indole
  • Tryptophan
  • Dimethylallyltranstransferase

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