Highly enantioselective synthesis of atropisomeric anilide derivatives through catalytic asymmetric N-arylation: Conformational analysis and application to asymmetric enolate chemistry

Osamu Kitagawa, Masatoshi Yoshikawa, Hajime Tanabe, Tomofumi Morita, Masashi Takahashi, Yasuo Dobashi, Takeo Taguchi

Research output: Contribution to journalArticle

96 Citations (Scopus)

Abstract

In the presence of (R)-DTBM-SEGPHOS-Pd(OAc)2 catalyst, N-arylation (aromatic amination) of various o-tert-butylanilides with p-iodonitrobenzene proceeds with high enantioselectivity (88-96% ee) to give atropisomeric N-(p-nitrophenyl)anilides having an N-C chiral axis in good yields. Atropisomeric anilide products highly prefer to exist as the E-rotamer which has trans-disposed o-tert-butylphenyl group and carbonyl oxygen. The application of the present catalytic enantioselective N-arylation to an intramolecular version gives atropisomeric lactam derivatives with high optical purity (92-98% ee). The reaction of the lithium enolate prepared from the atropisomeric anilide and lactam products with various alkyl halides gives α-alkylated products with high diastereoselectivity (diastereomer ratio = 13:1 to 46:1).

Original languageEnglish
Pages (from-to)12923-12931
Number of pages9
JournalJournal of the American Chemical Society
Volume128
Issue number39
DOIs
Publication statusPublished - 2006 Oct 4

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Highly enantioselective synthesis of atropisomeric anilide derivatives through catalytic asymmetric N-arylation: Conformational analysis and application to asymmetric enolate chemistry'. Together they form a unique fingerprint.

  • Cite this