Cu/Pd Synergistic Dual Catalysis: Asymmetric α-Allylation of an α-CF3 Amide

Akira Saito, Naoya Kumagai, Masakatsu Shibasaki

Research output: Contribution to journalArticlepeer-review

51 Citations (Scopus)

Abstract

Despite the burgeoning demand for fluorine-containing chemical entities, the construction of CF3-containing stereogenic centers has remained elusive. Herein, we report the strategic merger of CuI/base-catalyzed enolization of an α-CF3 amide and Pd0-catalyzed allylic alkylation in an enantioselective manner to deliver chiral building blocks bearing a stereogenic carbon center connected to a CF3, an amide carbonyl, and a manipulable allylic group. The phosphine complexes of CuI and Pd0 engage in distinct catalytic roles without ligand scrambling to render the dual catalysis operative to achieve asymmetric α-allylation of the amide. The stereoselective cyclization of the obtained α-CF3-γ,δ-unsaturated amides to give tetrahydropyran and γ-lactone-fused cyclopropane skeletons highlights the synthetic utility of the present catalytic method as a new entry to non-racemic CF3-containing compounds.

Original languageEnglish
Pages (from-to)5551-5555
Number of pages5
JournalAngewandte Chemie - International Edition
Volume56
Issue number20
DOIs
Publication statusPublished - 2017 May 8
Externally publishedYes

Keywords

  • allylic substitution
  • asymmetric catalysis
  • azaindolines
  • dual catalysis
  • organofluorine compounds

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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