Asymmetric Formal Synthesis of the Long-Acting DPP-4 Inhibitor Omarigliptin

J Org Chem. 2017 Sep 1;82(17):9023-9029. doi: 10.1021/acs.joc.7b01467. Epub 2017 Aug 14.

Abstract

A highly efficient asymmetric synthesis of the key tetrahydropyranol intermediate of DPP-4 inhibitor omarigliptin (1) is described. The successful development of a protecting-group- and precious-metal-free synthesis was achieved via the discovery of a practical asymmetric Henry reaction and the application of a one-pot nitro-Michael-lactolization-dehydration through-process. Other features of the synthesis include a highly efficient MsCl-mediated dehydration and a crystallization-induced dynamic resolution for exceptional ee and dr upgrade. The synthesis of this complex intermediate utilizes simple starting materials and proceeds in four linear steps.

MeSH terms

  • Dipeptidyl-Peptidase IV Inhibitors / chemical synthesis*
  • Dipeptidyl-Peptidase IV Inhibitors / chemistry
  • Heterocyclic Compounds, 2-Ring / chemical synthesis*
  • Heterocyclic Compounds, 2-Ring / chemistry
  • Molecular Structure
  • Pyrans / chemical synthesis*
  • Pyrans / chemistry

Substances

  • 2-(2,5-difluorophenyl)-5-(2-(methylsulfonyl)-2,6-dihydropyrrolo(3,4-c)pyrazol-5(4H)-yl)tetrahydro-2H-pyran-3-amine
  • Dipeptidyl-Peptidase IV Inhibitors
  • Heterocyclic Compounds, 2-Ring
  • Pyrans