Catalytic asymmetricaza-Morita-Baylis-Hillman reaction of methyl acrylate

Role of a bifunctional La(O- i Pr)3/linked-BINOL complex

Takafumi Yukawa, Bianca Seelig, Yingjie Xu, Hiroyuki Morimoto, Shigeki Matsunaga, Albrecht Berkessel, Masakatsu Shibasaki

Research output: Contribution to journalArticle

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Abstract

The catalytic asymmetric aza-Morita-Baylis-Hillman reaction using unactivated methyl acrylate is described. A simple Lewis acidic metal catalyst, such as La(OTf)3, was not suitable for the reaction, but rare earth metal alkoxide/linked-BINOL complexes possessing bifunctional Lewis acid and Brønsted base properties efficiently promoted the reaction in combination with an achiral nucleophilic organocatalyst. The combined use of a La(O-iPr)3/(S,S)-TMS-linked-BINOL complex with a catalytic amount of DABCO promoted the aza-Morita-Baylis-Hillman reaction of a broad range of N-diphenylphosphinoyl imines. Products from aryl, heteroaryl, and alkenyl imines were obtained in 67-99% yield and 81-95% ee. It is noteworthy that isomerizable alkyl imines could be employed as well, giving products in 78-89% yield and 94-98% ee. Initial rate kinetic studies as well as kinetic isotope effect experiments using α-deuterio-methyl acrylate support the importance of both the nucleophilicity of La-enolate and the Brønsted basicity of a La-catalyst for promoting the reaction.

Original languageEnglish
Pages (from-to)11988-11992
Number of pages5
JournalJournal of the American Chemical Society
Volume132
Issue number34
DOIs
Publication statusPublished - Sep 1 2010

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Imines
Catalysts
Kinetics
Rare Earth Metals
Alkalinity
Metals
Rare earths
Isotopes
Lewis Acids
Acids
Experiments
methyl acrylate
naphthol BINOL

All Science Journal Classification (ASJC) codes

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

Cite this

Catalytic asymmetricaza-Morita-Baylis-Hillman reaction of methyl acrylate : Role of a bifunctional La(O- i Pr)3/linked-BINOL complex. / Yukawa, Takafumi; Seelig, Bianca; Xu, Yingjie; Morimoto, Hiroyuki; Matsunaga, Shigeki; Berkessel, Albrecht; Shibasaki, Masakatsu.

In: Journal of the American Chemical Society, Vol. 132, No. 34, 01.09.2010, p. 11988-11992.

Research output: Contribution to journalArticle

Yukawa, Takafumi ; Seelig, Bianca ; Xu, Yingjie ; Morimoto, Hiroyuki ; Matsunaga, Shigeki ; Berkessel, Albrecht ; Shibasaki, Masakatsu. / Catalytic asymmetricaza-Morita-Baylis-Hillman reaction of methyl acrylate : Role of a bifunctional La(O- i Pr)3/linked-BINOL complex. In: Journal of the American Chemical Society. 2010 ; Vol. 132, No. 34. pp. 11988-11992.
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