Efficient Synthesis of Diaryl Quaternary Centers by Rh(II)/Xantphos Catalyzed Relay C-H Functionalization and Allylic Alkylation

Chemistry. 2023 Jan 12;29(3):e202202820. doi: 10.1002/chem.202202820. Epub 2022 Nov 24.

Abstract

A three-component reaction of N, N-disubstituted aniline, α-diazo ester, and an allylic electrophile has been realized by [Rh(II)]2 /Xantphos catalysis, providing a direct access to various aniline derivatives bearing diaryl allylic quaternary centers in good yields. The synthetic utility of this protocol was demonstrated by facile derivatization of the products for preparation of biologically relevant molecules and structural scaffolds, which offers a high potential for increasing the molecular diversity. Mechanistic studies identified α, α-diarylacetate species as an active intermediate, thereby revealing the presence of a C(sp2 )-H functionalization of aniline derivatives/allylic alkylation cascade in this attractive catalytic transformation.

Keywords: allylic units; diaryl quaternary centers; dirhodium(II) complex; relay catalysis; three-component reaction.

MeSH terms

  • Alkylation
  • Aniline Compounds*
  • Catalysis
  • Molecular Structure
  • Stereoisomerism

Substances

  • xantphos
  • aniline
  • Aniline Compounds