Sterically Demanding Oxidative Amidation of α-Substituted Malononitriles with Amines Using O2

Jing Li, Martin J. Lear, Yujiro Hayashi

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

An efficient amidation method between readily available 1,1-dicyanoalkanes and either chiral or nonchiral amines was realized simply with molecular oxygen and a carbonate base. This oxidative protocol can be applied to both sterically and electronically challenging substrates in a highly chemoselective, practical, and rapid manner. The use of cyclopropyl and thioether substrates support the radical formation of α-peroxy malononitrile species, which can cyclize to dioxiranes that can monooxygenate malononitrile α-carbanions to afford activated acyl cyanides capable of reacting with amine nucleophiles.

Original languageEnglish
Pages (from-to)9060-9064
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number31
DOIs
Publication statusPublished - 2016

Keywords

  • amides
  • amines
  • peroxides
  • radicals
  • reaction mechanisms

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Fingerprint Dive into the research topics of 'Sterically Demanding Oxidative Amidation of α-Substituted Malononitriles with Amines Using O<sub>2</sub>'. Together they form a unique fingerprint.

Cite this