Organometallic ruthenium complexes: Application in the olefination of carbonyl compounds

Filipe M. Pedro; Ana M. Santos; Walter Baratta; Fritz E. Kühn

doi:10.1021/om060508w

Organometallic ruthenium complexes: Application in the olefination of carbonyl compounds

Filipe M. Pedro, Ana M. Santos, Walter Baratta, Fritz E. Kühn

Associate Professorship of Molecular Catalysis

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

38 Scopus citations

Abstract

Ruthenium compounds of general formula Cp′RuX(PR₂R′) ₂ (Cp′ = η⁵-C₅H₅ (Cp), η⁵-C₉H₇ (Ind), η⁵C ₅(CH₃)₅ (Cp*); X = Cl, CF ₃C(O)O; R = C₆H₅ (Ph), C₆H ₄(CH₃) (m-tolyl); R′ = C₆H₅, C₆H₁₁ (Cy), C₆H₄(CH₃) (m-tolyl, o-tolyl)) are examined as catalysts for the aldehyde olefination starting from diazo compounds, phosphanes, and aldehydes. Cp*RuCl(PPh ₃)₂ is highly active for the olefmation of several aldehydes, displaying a very high E-selectivity, as well as for ketone olefination (with benzoic acid as cocatalyst). The reaction's mechanism is substantiated by the isolation of a catalytic active reaction species, namely, a mixed carbene/phosphane ruthenium complex, Cp*RuCl(=CHCO ₂Et)(PPh₃) (8). Spectroscopic studies reveal that the latter compound reacts with PPh₃ to produce the phosphorus ylide Ph₃P=CHCO₂Et, which further reacts with the aldehyde to produce the olefin.

Original language	English
Pages (from-to)	302-309
Number of pages	8
Journal	Organometallics
Volume	26
Issue number	2
DOIs	https://doi.org/10.1021/om060508w
State	Published - 15 Jan 2007

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@article{5adf196da15c4268be23598b26d49b3c,

title = "Organometallic ruthenium complexes: Application in the olefination of carbonyl compounds",

abstract = "Ruthenium compounds of general formula Cp′RuX(PR2R′) 2 (Cp′ = η5-C5H5 (Cp), η5-C9H7 (Ind), η5C 5(CH3)5 (Cp*); X = Cl, CF 3C(O)O; R = C6H5 (Ph), C6H 4(CH3) (m-tolyl); R′ = C6H5, C6H11 (Cy), C6H4(CH3) (m-tolyl, o-tolyl)) are examined as catalysts for the aldehyde olefination starting from diazo compounds, phosphanes, and aldehydes. Cp*RuCl(PPh 3)2 is highly active for the olefmation of several aldehydes, displaying a very high E-selectivity, as well as for ketone olefination (with benzoic acid as cocatalyst). The reaction's mechanism is substantiated by the isolation of a catalytic active reaction species, namely, a mixed carbene/phosphane ruthenium complex, Cp*RuCl(=CHCO 2Et)(PPh3) (8). Spectroscopic studies reveal that the latter compound reacts with PPh3 to produce the phosphorus ylide Ph3P=CHCO2Et, which further reacts with the aldehyde to produce the olefin.",

author = "Pedro, {Filipe M.} and Santos, {Ana M.} and Walter Baratta and K{\"u}hn, {Fritz E.}",

year = "2007",

month = jan,

day = "15",

doi = "10.1021/om060508w",

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volume = "26",

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journal = "Organometallics",

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publisher = "American Chemical Society",

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T1 - Organometallic ruthenium complexes

T2 - Application in the olefination of carbonyl compounds

AU - Pedro, Filipe M.

AU - Santos, Ana M.

AU - Baratta, Walter

AU - Kühn, Fritz E.

PY - 2007/1/15

Y1 - 2007/1/15

N2 - Ruthenium compounds of general formula Cp′RuX(PR2R′) 2 (Cp′ = η5-C5H5 (Cp), η5-C9H7 (Ind), η5C 5(CH3)5 (Cp*); X = Cl, CF 3C(O)O; R = C6H5 (Ph), C6H 4(CH3) (m-tolyl); R′ = C6H5, C6H11 (Cy), C6H4(CH3) (m-tolyl, o-tolyl)) are examined as catalysts for the aldehyde olefination starting from diazo compounds, phosphanes, and aldehydes. Cp*RuCl(PPh 3)2 is highly active for the olefmation of several aldehydes, displaying a very high E-selectivity, as well as for ketone olefination (with benzoic acid as cocatalyst). The reaction's mechanism is substantiated by the isolation of a catalytic active reaction species, namely, a mixed carbene/phosphane ruthenium complex, Cp*RuCl(=CHCO 2Et)(PPh3) (8). Spectroscopic studies reveal that the latter compound reacts with PPh3 to produce the phosphorus ylide Ph3P=CHCO2Et, which further reacts with the aldehyde to produce the olefin.

AB - Ruthenium compounds of general formula Cp′RuX(PR2R′) 2 (Cp′ = η5-C5H5 (Cp), η5-C9H7 (Ind), η5C 5(CH3)5 (Cp*); X = Cl, CF 3C(O)O; R = C6H5 (Ph), C6H 4(CH3) (m-tolyl); R′ = C6H5, C6H11 (Cy), C6H4(CH3) (m-tolyl, o-tolyl)) are examined as catalysts for the aldehyde olefination starting from diazo compounds, phosphanes, and aldehydes. Cp*RuCl(PPh 3)2 is highly active for the olefmation of several aldehydes, displaying a very high E-selectivity, as well as for ketone olefination (with benzoic acid as cocatalyst). The reaction's mechanism is substantiated by the isolation of a catalytic active reaction species, namely, a mixed carbene/phosphane ruthenium complex, Cp*RuCl(=CHCO 2Et)(PPh3) (8). Spectroscopic studies reveal that the latter compound reacts with PPh3 to produce the phosphorus ylide Ph3P=CHCO2Et, which further reacts with the aldehyde to produce the olefin.

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Organometallic ruthenium complexes: Application in the olefination of carbonyl compounds

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