Exploration of a Nitromethane-Carbonylation Strategy during Route Design of an Atropisomeric KRASG12C Inhibitor

J Org Chem. 2022 Feb 18;87(4):2075-2086. doi: 10.1021/acs.joc.1c01736. Epub 2021 Oct 15.

Abstract

Route design and proof of concept synthesis was conducted on a synthetically challenging atropisomeric KRASG12C inhibitor to support clinical API manufacture. Improvements to the synthesis of a chiral piperazine fragment gave reduced step count and streamlined protecting group strategy via the formation and methanol ring opening of an N-carboxy-anhydride (NCA). The complex atropisomeric nitroquinoline was accessed via an early stage salt-resolution followed by a formal two-part nitromethane-carbonylation, avoiding a high temperature Gould-Jacobs cyclization that previously led to atropisomer racemization. The substrate scope of the formal nitromethane-carbonylation strategy was further explored for a range of ortho-substituted bromo/iodo unprotected anilines.

MeSH terms

  • Methane / analogs & derivatives
  • Nitroparaffins
  • Proto-Oncogene Proteins p21(ras)*

Substances

  • Nitroparaffins
  • Proto-Oncogene Proteins p21(ras)
  • Methane
  • nitromethane