Electronic and steric effects of atropisomeric ligands Synphos® and Difluorphos® vs. BiNAPs in Rh(I)-catalyzed asymmetric Pauson-Khand reaction

Dong Eun Kim, Choong Choi, In Su Kim, Séverine Jeulin, Virginie Ratovelomanana-Vidal, Jean Pierre Genêt, Nakcheol Jeong

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

The electronic and steric effects of chiral biaryl diphosphine ligands on the Rh(I)-catalyzed asymmetric Pauson-Khand type reaction were examined. We demonstrated that enantioselectivity and reaction yield were influenced by the electronic density on phosphorus, the dihedral angle of ligands and the electronic density of the alkyne substrate. Ligands bearing a narrower dihedral angle than Binap, such as Synphos (L4) and Difluorphos (L5), were found to increase substantially the enantioselectivity of the reaction, compared to Binap-type ligands. Ligands having a deshielded phosphine, such as p-CF 3-Binap (L3) and Difluorphos (L5) provided better enantioselectivity than Binap, with reduced formation of side products, especially with electron-poor alkyne substrates.

Original languageEnglish
Pages (from-to)1999-2006
Number of pages8
JournalAdvanced Synthesis and Catalysis
Volume349
Issue number11-12
DOIs
Publication statusPublished - 2007 Aug 1

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Ligands
Enantioselectivity
phosphine
Alkynes
Dihedral angle
Bearings (structural)
Substrates
Phosphorus
Electrons

Keywords

  • Atropisomeric ligands
  • Electronic effects
  • Enantioselectivity
  • Pauson-Khand reaction
  • Steric effects

ASJC Scopus subject areas

  • Chemistry (miscellaneous)
  • Organic Chemistry
  • Catalysis

Cite this

Electronic and steric effects of atropisomeric ligands Synphos® and Difluorphos® vs. BiNAPs in Rh(I)-catalyzed asymmetric Pauson-Khand reaction. / Kim, Dong Eun; Choi, Choong; Kim, In Su; Jeulin, Séverine; Ratovelomanana-Vidal, Virginie; Genêt, Jean Pierre; Jeong, Nakcheol.

In: Advanced Synthesis and Catalysis, Vol. 349, No. 11-12, 01.08.2007, p. 1999-2006.

Research output: Contribution to journalArticle

Kim, Dong Eun ; Choi, Choong ; Kim, In Su ; Jeulin, Séverine ; Ratovelomanana-Vidal, Virginie ; Genêt, Jean Pierre ; Jeong, Nakcheol. / Electronic and steric effects of atropisomeric ligands Synphos® and Difluorphos® vs. BiNAPs in Rh(I)-catalyzed asymmetric Pauson-Khand reaction. In: Advanced Synthesis and Catalysis. 2007 ; Vol. 349, No. 11-12. pp. 1999-2006.
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AU - Kim, Dong Eun

AU - Choi, Choong

AU - Kim, In Su

AU - Jeulin, Séverine

AU - Ratovelomanana-Vidal, Virginie

AU - Genêt, Jean Pierre

AU - Jeong, Nakcheol

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AB - The electronic and steric effects of chiral biaryl diphosphine ligands on the Rh(I)-catalyzed asymmetric Pauson-Khand type reaction were examined. We demonstrated that enantioselectivity and reaction yield were influenced by the electronic density on phosphorus, the dihedral angle of ligands and the electronic density of the alkyne substrate. Ligands bearing a narrower dihedral angle than Binap, such as Synphos (L4) and Difluorphos (L5), were found to increase substantially the enantioselectivity of the reaction, compared to Binap-type ligands. Ligands having a deshielded phosphine, such as p-CF 3-Binap (L3) and Difluorphos (L5) provided better enantioselectivity than Binap, with reduced formation of side products, especially with electron-poor alkyne substrates.

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KW - Electronic effects

KW - Enantioselectivity

KW - Pauson-Khand reaction

KW - Steric effects

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