Catalytic asymmetric hydrogenation of 2,3,5-trisubstituted pyrroles

Ryoichi Kuwano, Manabu Kashiwabara, Masato Ohsumi, Hiroki Kusano

Research output: Contribution to journalArticle

100 Citations (Scopus)

Abstract

Catalytic asymmetric hydrogenation of N-Boc-protected pyrroles proceeded with high enantioselectivity by using a ruthenium catalyst modified with a trans-chelating chiral bisphosphine PhTRAP. The ruthenium catalyst prepared from Ru(η3-methallyl)2(cod) and (S,S)-(R,R)-PhTRAP in the presence of triethylamine was the most enantioselective for the asymmetric hydrogenation of methyl pyrrole-2-carboxylate, giving the desired (S)-proline derivative with 79% ee in 92% yield. Moreover, 2,3,5-trisubstituted pyrroles bearing a large substituent at the 5-position were hydrogenated with 93-99.7% ee. The asymmetric reduction of 4,5-dimethylpyrrole-2-carboxylate gave only all-cis isomer and created three chiral centers with high degree of stereocontrol in a single process. This is the first highly enantioselective reduction of pyrroles.

Original languageEnglish
Pages (from-to)808-809
Number of pages2
JournalJournal of the American Chemical Society
Volume130
Issue number3
DOIs
Publication statusPublished - Jan 23 2008

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Pyrroles
Hydrogenation
Ruthenium
Bearings (structural)
Catalysts
Enantioselectivity
Chelation
Isomers
Gadiformes
Derivatives
Proline

All Science Journal Classification (ASJC) codes

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

Cite this

Catalytic asymmetric hydrogenation of 2,3,5-trisubstituted pyrroles. / Kuwano, Ryoichi; Kashiwabara, Manabu; Ohsumi, Masato; Kusano, Hiroki.

In: Journal of the American Chemical Society, Vol. 130, No. 3, 23.01.2008, p. 808-809.

Research output: Contribution to journalArticle

Kuwano, Ryoichi ; Kashiwabara, Manabu ; Ohsumi, Masato ; Kusano, Hiroki. / Catalytic asymmetric hydrogenation of 2,3,5-trisubstituted pyrroles. In: Journal of the American Chemical Society. 2008 ; Vol. 130, No. 3. pp. 808-809.
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abstract = "Catalytic asymmetric hydrogenation of N-Boc-protected pyrroles proceeded with high enantioselectivity by using a ruthenium catalyst modified with a trans-chelating chiral bisphosphine PhTRAP. The ruthenium catalyst prepared from Ru(η3-methallyl)2(cod) and (S,S)-(R,R)-PhTRAP in the presence of triethylamine was the most enantioselective for the asymmetric hydrogenation of methyl pyrrole-2-carboxylate, giving the desired (S)-proline derivative with 79{\%} ee in 92{\%} yield. Moreover, 2,3,5-trisubstituted pyrroles bearing a large substituent at the 5-position were hydrogenated with 93-99.7{\%} ee. The asymmetric reduction of 4,5-dimethylpyrrole-2-carboxylate gave only all-cis isomer and created three chiral centers with high degree of stereocontrol in a single process. This is the first highly enantioselective reduction of pyrroles.",
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