A comparison of phosphaferrocene and phospharuthenocene ligands in Rh +-catalysed enamide hydrogenation reactions: Superior performance of the phospharuthenocene

Duncan Carmichael; Gabrielle Goldet; Jürgen Klankermayer; Louis Ricard; Nicolas Seeboth; Marek Stankevič

doi:10.1002/chem.200601715

A comparison of phosphaferrocene and phospharuthenocene ligands in Rh ⁺-catalysed enamide hydrogenation reactions: Superior performance of the phospharuthenocene

Duncan Carmichael
, Gabrielle Goldet
, Jürgen Klankermayer
, Louis Ricard
, Nicolas Seeboth
, Marek Stankevič

CNRS
RWTH Aachen University
University of Maria Curie-Skodowska

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

Abstract

Enantiopure Cp*-substituted 3.4-dimethyl-5-phenylphosphametallocene- 2-methanols (M=Fe, Ru) have been prepared from the corresponding 2-carboxy-(-)-menthylphospholide anion and elaborated into 2-CH ₂PPh₂ phosphametallocenes (13: M = Fe: 14: M = Ru) and 2-CH₂PtBuR substituted phospharuthenocenes (R = tBu, Me). The crystal structures of complexes [Rh(1,5-cod)(η²-L)]⁺BF ₄^- (L = 13, 14) reveal significantly different aryl group configurations. Comparative studies of the hydrogenation of para-substituted N-acetylcinnamate esters with these pre-catalysts show a superior performance for the phospharuthenocene derivative in terms of both rate and enantioselectivity.

Original language	English
Pages (from-to)	5492-5502
Number of pages	11
Journal	Chemistry - A European Journal
Volume	13
Issue number	19
DOIs	https://doi.org/10.1002/chem.200601715
Publication status	Published - 2 Aug 2007
Externally published	Yes

Keywords

Enamides
Enantioselectivity
Hydrogenation
Metallocenes
Phosphorus heterocycles

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10.1002/chem.200601715

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@article{81bbc195c52a46b8ae679b918c1cfdb6,

title = "A comparison of phosphaferrocene and phospharuthenocene ligands in Rh +-catalysed enamide hydrogenation reactions: Superior performance of the phospharuthenocene",

abstract = "Enantiopure Cp*-substituted 3.4-dimethyl-5-phenylphosphametallocene- 2-methanols (M=Fe, Ru) have been prepared from the corresponding 2-carboxy-(-)-menthylphospholide anion and elaborated into 2-CH 2PPh2 phosphametallocenes (13: M = Fe: 14: M = Ru) and 2-CH2PtBuR substituted phospharuthenocenes (R = tBu, Me). The crystal structures of complexes [Rh(1,5-cod)(η2-L)]+BF 4- (L = 13, 14) reveal significantly different aryl group configurations. Comparative studies of the hydrogenation of para-substituted N-acetylcinnamate esters with these pre-catalysts show a superior performance for the phospharuthenocene derivative in terms of both rate and enantioselectivity.",

keywords = "Enamides, Enantioselectivity, Hydrogenation, Metallocenes, Phosphorus heterocycles",

author = "Duncan Carmichael and Gabrielle Goldet and J{\"u}rgen Klankermayer and Louis Ricard and Nicolas Seeboth and Marek Stankevi{\v c}",

year = "2007",

month = aug,

day = "2",

doi = "10.1002/chem.200601715",

language = "English",

volume = "13",

pages = "5492--5502",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

number = "19",

}

A comparison of phosphaferrocene and phospharuthenocene ligands in Rh ⁺-catalysed enamide hydrogenation reactions: Superior performance of the phospharuthenocene. / Carmichael, Duncan; Goldet, Gabrielle; Klankermayer, Jürgen et al.
In: Chemistry - A European Journal, Vol. 13, No. 19, 02.08.2007, p. 5492-5502.

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

TY - JOUR

T1 - A comparison of phosphaferrocene and phospharuthenocene ligands in Rh +-catalysed enamide hydrogenation reactions

T2 - Superior performance of the phospharuthenocene

AU - Carmichael, Duncan

AU - Goldet, Gabrielle

AU - Klankermayer, Jürgen

AU - Ricard, Louis

AU - Seeboth, Nicolas

AU - Stankevič, Marek

PY - 2007/8/2

Y1 - 2007/8/2

N2 - Enantiopure Cp*-substituted 3.4-dimethyl-5-phenylphosphametallocene- 2-methanols (M=Fe, Ru) have been prepared from the corresponding 2-carboxy-(-)-menthylphospholide anion and elaborated into 2-CH 2PPh2 phosphametallocenes (13: M = Fe: 14: M = Ru) and 2-CH2PtBuR substituted phospharuthenocenes (R = tBu, Me). The crystal structures of complexes [Rh(1,5-cod)(η2-L)]+BF 4- (L = 13, 14) reveal significantly different aryl group configurations. Comparative studies of the hydrogenation of para-substituted N-acetylcinnamate esters with these pre-catalysts show a superior performance for the phospharuthenocene derivative in terms of both rate and enantioselectivity.

AB - Enantiopure Cp*-substituted 3.4-dimethyl-5-phenylphosphametallocene- 2-methanols (M=Fe, Ru) have been prepared from the corresponding 2-carboxy-(-)-menthylphospholide anion and elaborated into 2-CH 2PPh2 phosphametallocenes (13: M = Fe: 14: M = Ru) and 2-CH2PtBuR substituted phospharuthenocenes (R = tBu, Me). The crystal structures of complexes [Rh(1,5-cod)(η2-L)]+BF 4- (L = 13, 14) reveal significantly different aryl group configurations. Comparative studies of the hydrogenation of para-substituted N-acetylcinnamate esters with these pre-catalysts show a superior performance for the phospharuthenocene derivative in terms of both rate and enantioselectivity.

KW - Enamides

KW - Enantioselectivity

KW - Hydrogenation

KW - Metallocenes

KW - Phosphorus heterocycles

UR - https://www.scopus.com/pages/publications/34547368125

U2 - 10.1002/chem.200601715

DO - 10.1002/chem.200601715

M3 - Article

AN - SCOPUS:34547368125

SN - 0947-6539

VL - 13

SP - 5492

EP - 5502

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 19

ER -

A comparison of phosphaferrocene and phospharuthenocene ligands in Rh ⁺-catalysed enamide hydrogenation reactions: Superior performance of the phospharuthenocene

Abstract

Keywords

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