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

92 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
Externally publishedYes

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Anilides
Lactams
Derivatives
Amination
Enantioselectivity
Lithium
Catalysts
Oxygen

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Highly enantioselective synthesis of atropisomeric anilide derivatives through catalytic asymmetric N-arylation : Conformational analysis and application to asymmetric enolate chemistry. / Kitagawa, Osamu; Yoshikawa, Masatoshi; Tanabe, Hajime; Morita, Tomofumi; Takahashi, Masashi; Dobashi, Yasuo; Taguchi, Takeo.

In: Journal of the American Chemical Society, Vol. 128, No. 39, 04.10.2006, p. 12923-12931.

Research output: Contribution to journalArticle

Kitagawa, Osamu ; Yoshikawa, Masatoshi ; Tanabe, Hajime ; Morita, Tomofumi ; Takahashi, Masashi ; Dobashi, Yasuo ; Taguchi, Takeo. / Highly enantioselective synthesis of atropisomeric anilide derivatives through catalytic asymmetric N-arylation : Conformational analysis and application to asymmetric enolate chemistry. In: Journal of the American Chemical Society. 2006 ; Vol. 128, No. 39. pp. 12923-12931.
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AU - Kitagawa, Osamu

AU - Yoshikawa, Masatoshi

AU - Tanabe, Hajime

AU - Morita, Tomofumi

AU - Takahashi, Masashi

AU - Dobashi, Yasuo

AU - Taguchi, Takeo

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