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

doi:10.1002/adsc.200600623

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

35 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 language	English
Pages (from-to)	1999-2006
Number of pages	8
Journal	Advanced Synthesis and Catalysis
Volume	349
Issue number	11-12
DOIs	https://doi.org/10.1002/adsc.200600623
Publication status	Published - 2007 Aug

Keywords

Atropisomeric ligands
Electronic effects
Enantioselectivity
Pauson-Khand reaction
Steric effects

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1002/adsc.200600623

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title = "Electronic and steric effects of atropisomeric ligands Synphos{\textregistered} and Difluorphos{\textregistered} vs. BiNAPs in Rh(I)-catalyzed asymmetric Pauson-Khand reaction",

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.",

keywords = "Atropisomeric ligands, Electronic effects, Enantioselectivity, Pauson-Khand reaction, Steric effects",

author = "Kim, {Dong Eun} and Choong Choi and Kim, {In Su} and S{\'e}verine Jeulin and Virginie Ratovelomanana-Vidal and Gen{\^e}t, {Jean Pierre} and Nakcheol Jeong",

year = "2007",

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doi = "10.1002/adsc.200600623",

language = "English",

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T1 - Electronic and steric effects of atropisomeric ligands Synphos® and Difluorphos® vs. BiNAPs in Rh(I)-catalyzed asymmetric Pauson-Khand reaction

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

PY - 2007/8

Y1 - 2007/8

N2 - 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.

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.

KW - Atropisomeric ligands

KW - Electronic effects

KW - Enantioselectivity

KW - Pauson-Khand reaction

KW - Steric effects

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DO - 10.1002/adsc.200600623

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SN - 1615-4150

VL - 349

SP - 1999

EP - 2006

JO - Advanced Synthesis and Catalysis

JF - Advanced Synthesis and Catalysis

IS - 11-12

ER -

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

Abstract

Keywords

ASJC Scopus subject areas

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