Highly selective stereodivergent synthesis of separable amide rotamers, by using Pd chemistry, and their thermodynamic behavior

Nobutaka Ototake, Masashi Nakamura, Yasuo Dobashi, Haruhiko Fukaya, Osamu Kitagawa

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

By using Pd chemistry, a highly selective stereodivergent synthesis of separable amide rotamers was achieved. Allylation of 2,4,6-tri-tert-bu- tylanilides using a π-allyl-Pd catalyst gave N-allylated anilides with moderate-to-excellent Z-rotamer selectivity (ZIE = 3 to > 50). The Z-rotamer selectivity depends considerably on the substituent on the anilide substrates. On the other hand, the E rotamers of N-allylated 2,4,6-tri-tert-butylanilides were obtained with almost complete selectivity (E/Z > 50) through O-allylation of 2,4,6-tri-tert-butylanilides and the subsequent Pd II-catalyzed Claisen rearrangement of the resulting O-allyl imi-date. The prepared anilide rotamers changed to equilibrium mixtures in which the E rotamer was the major isomer when heated in toluene.

Original languageEnglish
Pages (from-to)5090-5095
Number of pages6
JournalChemistry - A European Journal
Volume15
Issue number20
DOIs
Publication statusPublished - 2009 May 11

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Anilides
Allylation
Amides
Thermodynamics
Isomers
Toluene
Catalysts
Substrates
2,4,6-tri-tert-butylanilide

Keywords

  • Allylation
  • Amides
  • Palladium
  • Rotamers stereodivergence

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Highly selective stereodivergent synthesis of separable amide rotamers, by using Pd chemistry, and their thermodynamic behavior. / Ototake, Nobutaka; Nakamura, Masashi; Dobashi, Yasuo; Fukaya, Haruhiko; Kitagawa, Osamu.

In: Chemistry - A European Journal, Vol. 15, No. 20, 11.05.2009, p. 5090-5095.

Research output: Contribution to journalArticle

Ototake, Nobutaka ; Nakamura, Masashi ; Dobashi, Yasuo ; Fukaya, Haruhiko ; Kitagawa, Osamu. / Highly selective stereodivergent synthesis of separable amide rotamers, by using Pd chemistry, and their thermodynamic behavior. In: Chemistry - A European Journal. 2009 ; Vol. 15, No. 20. pp. 5090-5095.
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AU - Kitagawa, Osamu

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