The Experts below are selected from a list of 108 Experts worldwide ranked by ideXlab platform
Jérôme Lacour - One of the best experts on this subject based on the ideXlab platform.
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Enantio- and regioselective CpRu-catalyzed
2015Co-Authors: Carroll Rearrangement, Martina Austeri, Frédéric Buron, Samuel Constant, Jérôme Lacour, David Linder, Jessica Müller, Simone TortoioliAbstract:Abstract: The addition of unstabilized carbonyl nucleophiles to allyl-metal fragments still represents a challenge for generating stereoselectively tertiary (and quaternary) stereogenic centers. In this context, the decarboxylative Carroll Rearrangement of secondary and tertiary allyl β-ketoesters is particularly interesting since chiral γ,δ-unsaturated ketones are obtained. Herein, we show that CpRu half-sandwich complexes can, in the presence of selected enantiopure diimine ligands, catalyze this transformation and afford complete conversions and decent level of enantiomeric excess. Zwitterionic adducts of a hexacoordinated phos-phorus anion and CpRu moieties were also associated and shown to generate air-, moisture-, and microwave-stable catalysts that can be readily purified and recycled. Carroll rearrange-ments of allylic β-ketoesters performed with these zwitterionic species occur with better regio- and enantioselectivity
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enantioselective cpru catalyzed Carroll Rearrangement ligand and metal source importance
European Journal of Organic Chemistry, 2008Co-Authors: David Linder, Frédéric Buron, Samuel Constant, Jérôme LacourAbstract:The addition of unstabilized carbonyl nucleophiles to unsymmetrical allyl-metal fragments still represents a challenge to generate stereogenic centers enantio- and regioselectively. In this context, the decarboxylative Carroll Rearrangement of allyl -keto esters is particularly interesting, since chiral,-unsaturated ketones are obtained. Herein, we show that CpRu half-sandwich complexes can, with selected enantiopure pyridine-monooxazoline ligands, catalyze this transformation and afford complete conversions along with good levels of regioselectivity and enantioselectivity. Even more challenging (electron-poor) substrates react (up to 86 % ee, branched/linear ratio 97:03). In addition, the use of an air-stable metal precursor, namely [CpRu(6-naphthalene)][PF6], allows the reaction to be carried out reproducibly evenin non-anhydrous THF with a catalyst loading as low as2 mol-%.
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Enantio‐ and Regioselective CpRu‐Catalyzed Carroll Rearrangement
ChemInform, 2008Co-Authors: Martina Austeri, Frédéric Buron, Samuel Constant, Jérôme Lacour, David Linder, Jessica Müller, Simone TortoioliAbstract:The addition of unstabilized carbonyl nucleophiles to allyl-metal fragments still represents a challenge for generating stereoselectively tertiary (and quaternary) stereogenic centers. In this context, the decarboxylative Carroll Rearrangement of secondary and tertiary allyl β-ketoesters is particularly interesting since chiral γ,δ-unsaturated ketones are obtained. Herein, we show that CpRu half-sandwich complexes can, in the presence of selected enantiopure diimine ligands, catalyze this transformation and afford complete conversions and decent level of enantiomeric excess. Zwitterionic adducts of a hexacoordinated phosphorus anion and CpRu moieties were also associated and shown to generate air-, moisture-, and microwave-stable catalysts that can be readily purified and recycled. Carroll Rearrangements of allylic β-ketoesters performed with these zwitterionic species occur with better regio- and enantioselectivity.
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Enantio- and regioselective CpRu-catalyzed Carroll Rearrangement
Pure and Applied Chemistry, 2008Co-Authors: Martina Austeri, Frédéric Buron, Samuel Constant, Jérôme Lacour, David Linder, Jessica Müller, Simone TortoioliAbstract:The addition of unstabilized carbonyl nucleophiles to allyl-metal fragments still represents a challenge for generating stereoselectively tertiary (and quaternary) stereogenic centers. In this context, the decarboxylative Carroll Rearrangement of secondary and tertiary allyl β-ketoesters is particularly interesting since chiral γ,δ-unsaturated ketones are obtained. Herein, we show that CpRu half-sandwich complexes can, in the presence of selected enantiopure diimine ligands, catalyze this transformation and afford complete conversions and decent level of enantiomeric excess. Zwitterionic adducts of a hexacoordinated phosphorus anion and CpRu moieties were also associated and shown to generate air-, moisture-, and microwave-stable catalysts that can be readily purified and recycled. Carroll Rearrangements of allylic β-ketoesters performed with these zwitterionic species occur with better regio- and enantioselectivity.
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Enantioselective CpRu‐Catalyzed Carroll Rearrangement – Ligand and Metal Source Importance
European Journal of Organic Chemistry, 2008Co-Authors: David Linder, Frédéric Buron, Samuel Constant, Jérôme LacourAbstract:The addition of unstabilized carbonyl nucleophiles to unsymmetrical allyl-metal fragments still represents a challenge to generate stereogenic centers enantio- and regioselectively. In this context, the decarboxylative Carroll Rearrangement of allyl -keto esters is particularly interesting, since chiral,-unsaturated ketones are obtained. Herein, we show that CpRu half-sandwich complexes can, with selected enantiopure pyridine-monooxazoline ligands, catalyze this transformation and afford complete conversions along with good levels of regioselectivity and enantioselectivity. Even more challenging (electron-poor) substrates react (up to 86 % ee, branched/linear ratio 97:03). In addition, the use of an air-stable metal precursor, namely [CpRu(6-naphthalene)][PF6], allows the reaction to be carried out reproducibly evenin non-anhydrous THF with a catalyst loading as low as2 mol-%.
Corinne E Augelli - One of the best experts on this subject based on the ideXlab platform.
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the Carroll Rearrangement 5 dodecen 2 one
Organic Syntheses, 2003Co-Authors: Stephen R Wilson, Corinne E AugelliAbstract:The Carroll Rearrangement: 5-dodecen-2-one intermediate: (1-Ethenyl)heptanyl 3-ketobutanoate. reactant: 3-Hydroxy-1-nonene (, 7.5 g, 0.053 mol) intermediate: 2-Carboxy-5-dodecen-2-one. product: 5-Dodecen-2-one. Keywords: acylation; addition, to CO; decarboxylation; esterification, unsubstituted monobasic acids; Rearrangements; Rearrangements; ring opening reactions; assay methods, for butyllithium, with diphenylacetic acid; lithium diisopropylamide (LDA), preparation of; tetrahydrofuran
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Organic Syntheses - The Carroll Rearrangement: 5‐Dodecen‐2‐one
Organic Syntheses, 2003Co-Authors: Stephen R Wilson, Corinne E AugelliAbstract:The Carroll Rearrangement: 5-dodecen-2-one intermediate: (1-Ethenyl)heptanyl 3-ketobutanoate. reactant: 3-Hydroxy-1-nonene (, 7.5 g, 0.053 mol) intermediate: 2-Carboxy-5-dodecen-2-one. product: 5-Dodecen-2-one. Keywords: acylation; addition, to CO; decarboxylation; esterification, unsubstituted monobasic acids; Rearrangements; Rearrangements; ring opening reactions; assay methods, for butyllithium, with diphenylacetic acid; lithium diisopropylamide (LDA), preparation of; tetrahydrofuran
Maurice Santelli - One of the best experts on this subject based on the ideXlab platform.
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Stereoselective Ester Dienolate Carroll Rearrangement: A New Approach to the Prelog‐Djerassi Lactone Framework.
ChemInform, 2010Co-Authors: Nicole Ouvrard, Jean Rodriguez, Maurice SantelliAbstract:Abstract The stereoselective ester dienolate Carroll Rearrangement of (E) and (Z)-allylic β-ketoesters has been studied and found to be a new attractive approach to the synthesis of the Prelog-Djerassi lactone and related compounds. The synthesis of the optically active lactone (−)-(2R, 3R, 4R, 6S)-1 as well as the formal synthesis of its natural occurring isomer are described.
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Stereochemistry of the Carroll Rearrangement: structure of (+)‐(2R)‐2‐[(1R,5R)‐5‐methyl‐2‐oxocyclopentyl]propionic acid, C9H14O3
Acta Crystallographica Section C Crystal Structure Communications, 1994Co-Authors: Nicole Ouvrard, Jean Rodriguez, Maurice Santelli, A. Baldy, J. Feneau-dupont, Jean-paul DeclercqAbstract:The configurations at the three chiral centres are R, R and R. The two substituents of the almost planar cyclopentanone are trans and the C2-C6-C10-C11 torsion angle is - 79 (1)-degrees.
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stereochemistry of the Carroll Rearrangement structure of 2r 2 1r 5r 5 methyl 2 oxocyclopentyl propionic acid c9h14o3
Acta Crystallographica Section C-crystal Structure Communications, 1994Co-Authors: Nicole Ouvrard, Jean Rodriguez, Maurice Santelli, A. Baldy, J Feneaudupont, Jean-paul DeclercqAbstract:The configurations at the three chiral centres are R, R and R. The two substituents of the almost planar cyclopentanone are trans and the C2-C6-C10-C11 torsion angle is - 79 (1)-degrees.
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Stereoselective ester dienolate Carroll Rearrangement: A new approach to the Prelog-Djerassi lactone framework
Tetrahedron Letters, 1993Co-Authors: Nicole Ouvrard, Jean Rodriguez, Maurice SantelliAbstract:Abstract The stereoselective ester dienolate Carroll Rearrangement of (E) and (Z)-allylic β-ketoesters has been studied and found to be a new attractive approach to the synthesis of the Prelog-Djerassi lactone and related compounds. The synthesis of the optically active lactone (−)-(2R, 3R, 4R, 6S)-1 as well as the formal synthesis of its natural occurring isomer are described.
Nicole Ouvrard - One of the best experts on this subject based on the ideXlab platform.
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Stereoselective Ester Dienolate Carroll Rearrangement: A New Approach to the Prelog‐Djerassi Lactone Framework.
ChemInform, 2010Co-Authors: Nicole Ouvrard, Jean Rodriguez, Maurice SantelliAbstract:Abstract The stereoselective ester dienolate Carroll Rearrangement of (E) and (Z)-allylic β-ketoesters has been studied and found to be a new attractive approach to the synthesis of the Prelog-Djerassi lactone and related compounds. The synthesis of the optically active lactone (−)-(2R, 3R, 4R, 6S)-1 as well as the formal synthesis of its natural occurring isomer are described.
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Stereochemistry of the Carroll Rearrangement: structure of (+)‐(2R)‐2‐[(1R,5R)‐5‐methyl‐2‐oxocyclopentyl]propionic acid, C9H14O3
Acta Crystallographica Section C Crystal Structure Communications, 1994Co-Authors: Nicole Ouvrard, Jean Rodriguez, Maurice Santelli, A. Baldy, J. Feneau-dupont, Jean-paul DeclercqAbstract:The configurations at the three chiral centres are R, R and R. The two substituents of the almost planar cyclopentanone are trans and the C2-C6-C10-C11 torsion angle is - 79 (1)-degrees.
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stereochemistry of the Carroll Rearrangement structure of 2r 2 1r 5r 5 methyl 2 oxocyclopentyl propionic acid c9h14o3
Acta Crystallographica Section C-crystal Structure Communications, 1994Co-Authors: Nicole Ouvrard, Jean Rodriguez, Maurice Santelli, A. Baldy, J Feneaudupont, Jean-paul DeclercqAbstract:The configurations at the three chiral centres are R, R and R. The two substituents of the almost planar cyclopentanone are trans and the C2-C6-C10-C11 torsion angle is - 79 (1)-degrees.
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Stereoselective ester dienolate Carroll Rearrangement: A new approach to the Prelog-Djerassi lactone framework
Tetrahedron Letters, 1993Co-Authors: Nicole Ouvrard, Jean Rodriguez, Maurice SantelliAbstract:Abstract The stereoselective ester dienolate Carroll Rearrangement of (E) and (Z)-allylic β-ketoesters has been studied and found to be a new attractive approach to the synthesis of the Prelog-Djerassi lactone and related compounds. The synthesis of the optically active lactone (−)-(2R, 3R, 4R, 6S)-1 as well as the formal synthesis of its natural occurring isomer are described.
Stephen R Wilson - One of the best experts on this subject based on the ideXlab platform.
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the Carroll Rearrangement 5 dodecen 2 one
Organic Syntheses, 2003Co-Authors: Stephen R Wilson, Corinne E AugelliAbstract:The Carroll Rearrangement: 5-dodecen-2-one intermediate: (1-Ethenyl)heptanyl 3-ketobutanoate. reactant: 3-Hydroxy-1-nonene (, 7.5 g, 0.053 mol) intermediate: 2-Carboxy-5-dodecen-2-one. product: 5-Dodecen-2-one. Keywords: acylation; addition, to CO; decarboxylation; esterification, unsubstituted monobasic acids; Rearrangements; Rearrangements; ring opening reactions; assay methods, for butyllithium, with diphenylacetic acid; lithium diisopropylamide (LDA), preparation of; tetrahydrofuran
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Organic Syntheses - The Carroll Rearrangement: 5‐Dodecen‐2‐one
Organic Syntheses, 2003Co-Authors: Stephen R Wilson, Corinne E AugelliAbstract:The Carroll Rearrangement: 5-dodecen-2-one intermediate: (1-Ethenyl)heptanyl 3-ketobutanoate. reactant: 3-Hydroxy-1-nonene (, 7.5 g, 0.053 mol) intermediate: 2-Carboxy-5-dodecen-2-one. product: 5-Dodecen-2-one. Keywords: acylation; addition, to CO; decarboxylation; esterification, unsubstituted monobasic acids; Rearrangements; Rearrangements; ring opening reactions; assay methods, for butyllithium, with diphenylacetic acid; lithium diisopropylamide (LDA), preparation of; tetrahydrofuran