Atom Economic Ruthenium-Catalyzed Synthesis of Bulky beta-Oxo Esters

Janine Jeschke, Marcus Korb, Tobias Rueffer, Christian Gaebler, Heinrich Lang

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Ruthenium complexes with the formulae Ru(CO)(2)(PR3)(2)(O2CPh)(2) [6a-h; R=n-Bu, p-MeO-C6H4, p-Me-C6H4, Ph, p-Cl-C6H4, m-Cl-C6H4, p-CF3-C6H4, m,m'-(CF3)(2)C6H3] were prepared by treatment of triruthenium dodecacarbonyl [Ru-3(CO)(12)] with the respective phosphine and benzoic acid or by the conversion of Ru(CO)(3)(PR3)(2) (8e-h) with benzoic acid. During the preparation of 8, ruthenium hydride complexes of type Ru(CO)(PR3)(3)(H)(2) (9g, h) could be isolated as side products. The molecular structures of the newly synthesized complexes in the solid state are discussed. Compounds 6a-h were found to be highly effective catalysts in the addition of carboxylic acids to propargylic alcohols to give valuable beta-oxo esters. The catalyst screening revealed a considerably influence of the phosphine's electronic nature on the resulting activities. The best performances were obtained with complexes 6g and 6h, featuring electron-withdrawing phosphine ligands. Additionally, catalyst 6g is very active in the conversion of sterically demanding substrates, leading to a broad substrate scope. The catalytic preparation of simple as well as challenging substrates succeeds with catalyst 6g in yields that often exceed those of established literature systems. Furthermore, the reactions can be carried out with catalyst loadings down to 0.1 mol% and reaction temperatures down to 50 degrees C.

Original languageEnglish
Pages (from-to)4069-4081
Number of pages13
JournalADVANCED SYNTHESIS & CATALYSIS
Volume357
Issue number18
DOIs
Publication statusPublished - 14 Dec 2015
Externally publishedYes

Cite this

Jeschke, Janine ; Korb, Marcus ; Rueffer, Tobias ; Gaebler, Christian ; Lang, Heinrich. / Atom Economic Ruthenium-Catalyzed Synthesis of Bulky beta-Oxo Esters. In: ADVANCED SYNTHESIS & CATALYSIS. 2015 ; Vol. 357, No. 18. pp. 4069-4081.
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abstract = "Ruthenium complexes with the formulae Ru(CO)(2)(PR3)(2)(O2CPh)(2) [6a-h; R=n-Bu, p-MeO-C6H4, p-Me-C6H4, Ph, p-Cl-C6H4, m-Cl-C6H4, p-CF3-C6H4, m,m'-(CF3)(2)C6H3] were prepared by treatment of triruthenium dodecacarbonyl [Ru-3(CO)(12)] with the respective phosphine and benzoic acid or by the conversion of Ru(CO)(3)(PR3)(2) (8e-h) with benzoic acid. During the preparation of 8, ruthenium hydride complexes of type Ru(CO)(PR3)(3)(H)(2) (9g, h) could be isolated as side products. The molecular structures of the newly synthesized complexes in the solid state are discussed. Compounds 6a-h were found to be highly effective catalysts in the addition of carboxylic acids to propargylic alcohols to give valuable beta-oxo esters. The catalyst screening revealed a considerably influence of the phosphine's electronic nature on the resulting activities. The best performances were obtained with complexes 6g and 6h, featuring electron-withdrawing phosphine ligands. Additionally, catalyst 6g is very active in the conversion of sterically demanding substrates, leading to a broad substrate scope. The catalytic preparation of simple as well as challenging substrates succeeds with catalyst 6g in yields that often exceed those of established literature systems. Furthermore, the reactions can be carried out with catalyst loadings down to 0.1 mol{\%} and reaction temperatures down to 50 degrees C.",
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Atom Economic Ruthenium-Catalyzed Synthesis of Bulky beta-Oxo Esters. / Jeschke, Janine; Korb, Marcus; Rueffer, Tobias; Gaebler, Christian; Lang, Heinrich.

In: ADVANCED SYNTHESIS & CATALYSIS, Vol. 357, No. 18, 14.12.2015, p. 4069-4081.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Atom Economic Ruthenium-Catalyzed Synthesis of Bulky beta-Oxo Esters

AU - Jeschke, Janine

AU - Korb, Marcus

AU - Rueffer, Tobias

AU - Gaebler, Christian

AU - Lang, Heinrich

PY - 2015/12/14

Y1 - 2015/12/14

N2 - Ruthenium complexes with the formulae Ru(CO)(2)(PR3)(2)(O2CPh)(2) [6a-h; R=n-Bu, p-MeO-C6H4, p-Me-C6H4, Ph, p-Cl-C6H4, m-Cl-C6H4, p-CF3-C6H4, m,m'-(CF3)(2)C6H3] were prepared by treatment of triruthenium dodecacarbonyl [Ru-3(CO)(12)] with the respective phosphine and benzoic acid or by the conversion of Ru(CO)(3)(PR3)(2) (8e-h) with benzoic acid. During the preparation of 8, ruthenium hydride complexes of type Ru(CO)(PR3)(3)(H)(2) (9g, h) could be isolated as side products. The molecular structures of the newly synthesized complexes in the solid state are discussed. Compounds 6a-h were found to be highly effective catalysts in the addition of carboxylic acids to propargylic alcohols to give valuable beta-oxo esters. The catalyst screening revealed a considerably influence of the phosphine's electronic nature on the resulting activities. The best performances were obtained with complexes 6g and 6h, featuring electron-withdrawing phosphine ligands. Additionally, catalyst 6g is very active in the conversion of sterically demanding substrates, leading to a broad substrate scope. The catalytic preparation of simple as well as challenging substrates succeeds with catalyst 6g in yields that often exceed those of established literature systems. Furthermore, the reactions can be carried out with catalyst loadings down to 0.1 mol% and reaction temperatures down to 50 degrees C.

AB - Ruthenium complexes with the formulae Ru(CO)(2)(PR3)(2)(O2CPh)(2) [6a-h; R=n-Bu, p-MeO-C6H4, p-Me-C6H4, Ph, p-Cl-C6H4, m-Cl-C6H4, p-CF3-C6H4, m,m'-(CF3)(2)C6H3] were prepared by treatment of triruthenium dodecacarbonyl [Ru-3(CO)(12)] with the respective phosphine and benzoic acid or by the conversion of Ru(CO)(3)(PR3)(2) (8e-h) with benzoic acid. During the preparation of 8, ruthenium hydride complexes of type Ru(CO)(PR3)(3)(H)(2) (9g, h) could be isolated as side products. The molecular structures of the newly synthesized complexes in the solid state are discussed. Compounds 6a-h were found to be highly effective catalysts in the addition of carboxylic acids to propargylic alcohols to give valuable beta-oxo esters. The catalyst screening revealed a considerably influence of the phosphine's electronic nature on the resulting activities. The best performances were obtained with complexes 6g and 6h, featuring electron-withdrawing phosphine ligands. Additionally, catalyst 6g is very active in the conversion of sterically demanding substrates, leading to a broad substrate scope. The catalytic preparation of simple as well as challenging substrates succeeds with catalyst 6g in yields that often exceed those of established literature systems. Furthermore, the reactions can be carried out with catalyst loadings down to 0.1 mol% and reaction temperatures down to 50 degrees C.

KW - homogeneous catalysis

KW - phosphines

KW - propargylic alcohols

KW - ruthenium

KW - solid state structure

KW - METAL VINYLIDENE COMPLEXES

KW - C BOND FORMATION

KW - CARBOXYLIC-ACIDS

KW - TERMINAL ALKYNES

KW - ENOL ESTERS

KW - STEREOSELECTIVE ADDITION

KW - PROPARGYLIC ALCOHOLS

KW - EFFICIENT SYNTHESIS

KW - FACILE SYNTHESIS

KW - PLATINUM METALS

U2 - 10.1002/adsc.201500712

DO - 10.1002/adsc.201500712

M3 - Article

VL - 357

SP - 4069

EP - 4081

JO - ADVANCED SYNTHESIS & CATALYSIS

JF - ADVANCED SYNTHESIS & CATALYSIS

SN - 1615-4150

IS - 18

ER -