Synthesis of the 6-azaindole containing HIV-1 attachment inhibitor pro-drug, BMS-663068

J Org Chem. 2014 Sep 19;79(18):8757-67. doi: 10.1021/jo5016008. Epub 2014 Sep 5.

Abstract

The development of a short and efficient synthesis of a complex 6-azaindole, BMS-663068, is described. Construction of the 6-azaindole core is quickly accomplished starting from a simple pyrrole, via a regioselective Friedel-Crafts acylation, Pictet-Spengler cyclization, and a radical-mediated aromatization. The synthesis leverages an unusual heterocyclic N-oxide α-bromination to functionalize a critical C-H bond, enabling a highly regioselective copper-mediated Ullmann-Goldberg-Buchwald coupling to install a challenging triazole substituent. This strategy resulted in an efficient 11 step linear synthesis of this complex clinical candidate.

MeSH terms

  • Anti-HIV Agents / chemical synthesis*
  • Anti-HIV Agents / pharmacology*
  • Aza Compounds / chemical synthesis*
  • Aza Compounds / chemistry
  • Aza Compounds / pharmacology*
  • Cyclic N-Oxides / chemistry
  • HIV-1 / drug effects
  • Halogenation
  • Humans
  • Indoles / chemical synthesis*
  • Indoles / chemistry
  • Indoles / pharmacology*
  • Molecular Structure
  • Organophosphates / chemical synthesis*
  • Organophosphates / chemistry
  • Organophosphates / pharmacology*
  • Piperazines / chemical synthesis*
  • Piperazines / chemistry
  • Piperazines / pharmacology*
  • Prodrugs
  • Pyrroles / chemistry
  • Stereoisomerism
  • Virus Attachment / drug effects*

Substances

  • 6-azaindole
  • Anti-HIV Agents
  • Aza Compounds
  • Cyclic N-Oxides
  • Indoles
  • Organophosphates
  • Piperazines
  • Prodrugs
  • Pyrroles
  • fostemsavir