One-Pot Synthesis of Enantioenriched β-Amino Secondary Amides via an Enantioselective [4+2] Cycloaddition Reaction of Vinyl Azides with N-Acyl Imines Catalyzed by a Chiral Brønsted Acid

Taishi Nakanishi, Jun Kikuchi, Atsushi Kaga, Shunsuke Chiba, Masahiro Terada

Research output: Contribution to journalArticle

Abstract

A catalytic enantioselective synthesis of β-amino secondary amides was achieved using vinyl azides as the enamine-type nucleophile and chiral N-Tf phosphoramide as the chiral Brønsted acid catalyst through a five-step sequential transformation in one pot. The established sequential transformation involves an enantioselective [4+2] cycloaddition reaction of vinyl azides with N-acyl imines as the key stereo-determining step that is efficiently accelerated by a chiral N-Tf phosphoramide catalyst in a highly enantioselective manner in most cases. Further generation of the iminodiazonium ion intermediate through ring opening of the cycloaddition product and subsequent skeletal rearrangement involving Schmidt-type 1,2-aryl group migration followed by recyclization of the resulting nitrilium ion were also initiated by the same acid catalyst. Final acid hydrolysis of the recyclized products in the same pot gave rise to enantioenriched β-amino amides through C−C bond formation at the α-position of the secondary amides.

Original languageEnglish
Pages (from-to)8230-8234
Number of pages5
JournalChemistry - A European Journal
Volume26
Issue number37
DOIs
Publication statusPublished - 2020 Jul 2

Keywords

  • Brønsted acid
  • enantioselectivity
  • vinyl azides
  • [4+2] cycloaddition
  • β-amino amides

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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