0000000001305205
AUTHOR
Régine Amardeil
showing 36 related works from this author
Progress in palladium-based catalytic systems for the sustainable synthesis of annulated heterocycles: a focus on indole backbones
2012
BIOVERT+LDJ; A survey highlighting the most recent palladium catalytic systems produced and their performances for progress in direct synthesis of indole backbones by heterocarbocyclization of reactive substrates is provided. The discussion is developed in relation with the principles of sustainable chemistry concerning atom and mass economy. In this respect, the general convergent character of the syntheses is of particular interest (one-pot, domino, cascade or tandem reactions), and the substrates accessibility and reactivity, together with the final waste production, are also important. This critical review clearly indicates that the development of ligand chemistry, mainly phosphines and…
Use of a bulky phosphine of weak σ-donicity with palladium as a versatile and highly-active catalytic system: allylation and arylation coupling react…
2005
Abstract Carbon–carbon(sp2–sp2 and sp1–sp2) and carbon–nitrogen (nucleophilic allylation) coupling processes are promoted by a catalytic system containing [PdCl(η3–C3H5)]2 with the new ferrocenyl bis(difurylphosphine) 1,1′-bis[di(5-methyl-2-furyl)phosphino]ferrocene, Fc[P(FuMe)2]2. Starting from aryl bromides or allylic acetates this versatile catalyst system may be used at low palladium loadings (10−1–10−4 mol%) in some Heck, Suzuki, Sonogashira and allylic amination reactions to give cross-coupled products in excellent yield. Remarkably high activity is obtained in allylic substitution reactions, providing a significant impetus for the development of bulky phosphines possessing weak σ-don…
Different coordination modes of a 1,1′,2,2′-ferrocenyltetraphosphine: Bi- and tri-dentate behaviour with group 6 and 7 transition metals
2002
The behaviour of 1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di(tert-butyl)ferrocene (1), acting as a homoannular or heteroannular ligand, has been studied. Due to the cisoid disposition of the phosphino groups of each ring, different coordination modes are observed. With group 6 metal carbonyls, M(CO)6, the tetraphosphine acts exclusively as a tridentate ligand. In contrast, the reaction with MnCp(CO)3 leads to complexes showing 1,1′ and 1,2 bidentate coordination modes. All these complexes have been characterised by 1H and 31P NMR spectroscopy. The molecular structures of the molybdenum complex [(1)Mo(CO)3] (2b) and the 1,1′ manganese complex [(1)MnCp(CO)] (3) have been established by X-ra…
Highly Functionalized Ferrocenes
2020
International audience; Ferrocene is unique among organometallic compounds, and serves notably as a versatile platform towards the production of ligands useful to promote transition metals chemistry. A general limiting aspect of the synthesis of ferrocene derivatives is the efficient access to sophisticated highly functionalized polysubstituted ferrocenes, i. e. bearing four or more substituents replacing hydrogen atoms on the cyclopentadienyl rings. These ferrocene derivatives can bear various functional or/and structuring spectator substituents. Their preparation involves synthetic difficulties resulting from the need of multiple functionalizations coexisting altogether, and satisfying fu…
General route to dissymmetric heteroannular-functionalized ferrocenyl 1,2-diphosphines: selective synthesis and characterization of a new class of tr…
2006
Several monosubstituted-cyclopentadienyl anions (A-Li) and [1,2-bis(diphenylphosphino)-4-tert-butylcyclopentadienyl]lithium (B-Li) react with FeCl2 to afford a novel class of multidentate ferroceny...
1,1′,2,2′-Tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene, a new cisoid arrangement of phosphino groups
2001
Abstract The action of two equivalents of 1,2-bis(diphenylphosphino)-4- tert -butylcyclopentadienyllithium on FeCl 2 led to the corresponding 1,1′,2,2′-tetraphosphinoferrocene. The X-ray structure of this bulky ferrocene is described. The spectroscopic results reveal a conformational chirality with a cisoid disposition of the phosphino groups. The first results about the complexation with representative elements of Group IX and X (Rh, Pd, Ir) are reported.
Enlarging the family of ferrocenylphosphine dinuclear rhodium complexes: synthesis and X-ray structure of a novel “A-frame”-type trimetallic Rh/Fe/Rh…
2004
Abstract The symmetrically substituted ligand 1,1 ′ -bis[di(5-methyl-2-furyl)phosphino]ferrocene ( 1 ) has been obtained from the bromophosphine BrP(Fu Me ) 2 and the dilithioferrocene/TMEDA adduct. The quantitative addition of this ferrocene derivative to the tetracarbonyl dimer [(CO) 4 Rh 2 {μ-(S t Bu) 2 }] leads, through decarbonylation, to the dinuclear rhodium complex [(CO) 2 Rh 2 {μ-(S t Bu) 2 }{μ- P , P -Fc[P(Fu Me ) 2 ] 2 }] ( 2 ) in high yield. A X-ray structure [ orthorhombic , space group P 2 1 2 1 2 1 ; a =11.2982(2) A, b =13.3165(3) A, c =27.2687(7) A] and the solution multinuclear NMR characterization are reported, which show that the rare “quasi-closed bridging” A-frame struc…
ChemInform Abstract: Progress in Palladium-Based Catalytic Systems for the Sustainable Synthesis of Annulated Heterocycles: A Focus on Indole Backbon…
2012
A survey highlighting the most recent palladium catalytic systems produced and their performances for progress in direct synthesis of indole backbones by heterocarbocyclization of reactive substrates is provided. The discussion is developed in relation with the principles of sustainable chemistry concerning atom and mass economy. In this respect, the general convergent character of the syntheses is of particular interest (one-pot, domino, cascade or tandem reactions), and the substrates accessibility and reactivity, together with the final waste production, are also important. This critical review clearly indicates that the development of ligand chemistry, mainly phosphines and carbenes, in…
Synthesis and characterisation of a new class of phosphine-phosphonite ferrocenediyl dinuclear rhodium complexes
2004
We previously reported the easy access to mixed ferrocenediyl ligands bearing phosphine and phosphonite moieties. Using this strategy, a new enantiopure phosphine-menthylphosphonite ferrocenediyl has been synthesised. This mixed ligand leads to original unsymmetrical dinuclear rhodium coordination-complexes. One example of this new class of “quasi-close bridging A frame” dinuclear rhodium complexes, fully characterised by multinuclear 1H, 13C, 31P and 103Rh NMR and optical rotation measurements, is presented. Preliminary tests have shown an activity improvement in the hydroformylation of oct-1-ene using the phosphine-menthylphosphonite ferrocenediyl auxiliary compared to known phosphine-pho…
"Through-space" nuclear spin-spin J(PP) coupling in tetraphosphine ferrocenyl derivatives: a (31)P NMR and X-ray structure correlation study for coor…
2004
Herein, we report on (31)P(31)P solution-phase "through-space" nuclear spin-spin coupling constants (J(PP)) from a novel family of organometallic tetraphosphine nickel and palladium complexes. These J(PP) constants were accurately determined through NMR iterative simulation based on the second-order spectra obtained for the compounds. The corresponding solid-state X-ray structures of the complexes were determined, and the "through-space" P.P distances are reported. Due to the blocked conformation of the species in solution, a qualitative and semiquantitative experimental correlation is obtained, which links the geometric parameters and the intensity of the corresponding P.P coupling constan…
Catalytic Efficiency of a New Tridentate Ferrocenyl Phosphine Auxiliary: Sonogashira Cross-Coupling Reactions of Alkynes with Aryl Bromides and Chlor…
2005
[structure: see text] The catalytic activity in Sonogashira cross-coupling reactions of alkynes with a variety of aryl halides (including chlorides) using a multidentate ferrocenyl phosphine is presented. The novel mixed ferrocenyl aryl/alkyl triphosphine is thermally stable and insensitive to air or moisture, and its robustness allows aryl alkynylation at 10(-1) to 10(-4) mol % catalyst loadings with TONs up to 250,000. Copper-free coupling using phenylacetylene is also accessible in good yield.
Structural diversity in coordination chemistry of tridentate and tetradentate polyphosphines of Group 6 to 10 transition metal complexes
2003
Abstract Tridentate and tetradentate polyphosphines offer a huge variety of coordination modes to transition metals which lead, depending on the metal, to very different structural features in the resulting complexes. Steric effects being crucial in metal–phosphine complexes reactivity, a good knowledge of the molecular structures of the species is required both in the solid state and in solution. This article reviews from a structural point of view the monometallic and symmetrical homobimetallic complexes of the transition elements of Group 6 to 10 with tridentate and tetradentate phosphines. Concerning the classical triphosphines and tetraphosphines, emphasis was put on advances reported …
Congested ferrocenyl polyphosphanes bearing electron-donating or electron-withdrawing phosphanyl groups: assessment of metallocene conformation from …
2011
International audience; The synthesis of novel substituted cyclopentadienyl salts that incorporate both a congested branched alkyl group (tert-butyl, (triphenyl)methyl, or tri(4-tert-butyl)phenylmethyl) and a phosphanyl group is reported. The introduction of either electron-withdrawing or electron-donating substituents (furyl, i-propyl, cyclohexyl, tert-butyl) on P atoms was generally achieved in high yield. The modular synthesis of ferrocenyl polyphosphanes from an assembly of these cyclopentadienyl salts was investigated, leading to the formation of new triphosphanes (denoted as 9-12) and diphosphanes (denoted as 14-16). The resulting phosphanes are not sensitive to air or moisture, even …
Diphosphines of dppf-Type Incorporating Electron-Withdrawing Furyl Moieties Substantially Improve the Palladium-Catalysed Amination of Allyl Acetates
2005
Highly active Pd/diphosphine catalytic systems incorporating new, air-stable ferrocenyl-furylphosphines allow nucleophilic allylic amination at room temperature with unprecedented turnover frequencies. For instance, in the presence of 0.01 mol % catalyst the coupling of aniline to allyl acetate occurs at a TOF of more than 10,000 h - 1 ; even the addition of the less nucleophile morpholine to allyl acetate is observed with a TOF of 4250 h - 1 . The amination of the sterically demanding geranyl acetate, a monoterpene derivative of interest in the flavour industry, at low catalyst loadings demonstrates the scope of this methodology, which provides in addition noticeable advantages in terms of…
Gold(I) Complexes of Ferrocenyl Polyphosphines: Aurophilic Gold Chloride Formation and Phosphine-Concerted Shuttling of a Dinuclear [ClAu···AuCl] Fra…
2016
International audience; A smart steric control of the metallocene backbone in bis- and poly(phosphino)ferrocene ligands favors intramolecular aurophilic interactions between [AuCl] fragments in polynuclear gold(I) complexes. We synthesized and characterized by multinuclear NMR and X-ray diffraction analysis mono-, di-, and polynuclear gold complexes of constrained ferrocenyl diphosphines, which bear either bulky tert-butyl groups or more flexible siloxane substituents at the cyclopentadienyl rings. The complexes meso-1,1'-bis-(diphenylphosphino)-3,3'-di-tert-butylferrocene (4-m), rac-1,1'-bis[bis-(5-methy1-2-furyl)phosphino]-3,3'-di-tert-butyfferrocene (5-r), and rac-1,1'-bis ( diphenylphos…
{1,1′-Bis[bis(5-methyl-2-furyl)phosphino]ferrocene-κ2P,P′}dichloroplatinum(II) dichloromethane hemisolvate
2005
The synthesis of the title compound, [FePtCl2(C15H14O2P)2]·0.5CH2Cl2, has been achieved by reacting PtCl2(PhCN)2 with the 1,1′-bis[bis(5-methyl-2-furyl)phosphino]ferrocene chelating ligand. The environment at the Pt atom can be described as distorted square-planar, with two cis-Cl atoms and two cis-P atoms.
New concepts in multidentate ligand chemistry: effects of multidentarity on catalytic and spectroscopic properties of ferrocenyl polyphosphines.
2008
This tutorial review devoted to ligand chemistry deals with the design and properties of ferrocenyl polyphosphines, an original class of multidentate ligands. The development of a varied library of ferrocenyl tetra-, tri- and diphosphine ligands is reviewed. The multidentate nature of these species has led to unique spectroscopic and catalytic properties, in which the spatial proximity of phosphorus atoms is crucial. Regarding their catalytic applications, the key issues of catalyst longevity and ultralow catalyst loadings are discussed. Another part is concerned with fundamental advances gained in physical chemistry for structure elucidation by the study of the intriguing “through-space” N…
ChemInform Abstract: New Concepts in Multidentate Ligand Chemistry: Effects of Multidentarity on Catalytic and Spectroscopic Properties of Ferrocenyl…
2008
This tutorial review devoted to ligand chemistry deals with the design and properties of ferrocenyl polyphosphines, an original class of multidentate ligands. The development of a varied library of ferrocenyl tetra-, tri- and diphosphine ligands is reviewed. The multidentate nature of these species has led to unique spectroscopic and catalytic properties, in which the spatial proximity of phosphorus atoms is crucial. Regarding their catalytic applications, the key issues of catalyst longevity and ultralow catalyst loadings are discussed. Another part is concerned with fundamental advances gained in physical chemistry for structure elucidation by the study of the intriguing “through-space” N…
First copper(I) ferrocenyltetraphosphine complexes: possible involvement in Sonogashira cross-coupling reaction ?
2008
Preparation and characterization of the first examples of copper(I) ferrocenylpolyphosphine complexes are reported. The molecular structure of complex {P,P′,P′′-[1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene]iodocopper(I)} (1) was solved by X-ray diffraction studies, and its fluxional behavior in solution was investigated by VT-31P NMR; both revealed a net triligated coordination preference of the ferrocenyl tetraphosphine Fc(P)4tBu with copper. The tetradentate ligand is an active auxiliary in Sonogashira alkynylation; therefore the general question of copper as a competitive coordination partner in the Pd/Cu-catalyzed Sonogashira reaction was raised and discussed. Elec…
Highly Functionalized Brønsted Acidic/Lewis Basic Hybrid Ferrocene Ligands: Synthesis and Coordination Chemistry
2019
International audience; A general challenging issue in the synthesis of hemilabile ferrocene ligands is the access to highly functionalized ferrocene starting materials. These can bear donor/acceptor atoms, additional functional and structuring spectator substituents, but the preparation of such species poses general synthetic difficulties. We report herein alternative synthetic routes to hybrid ferrocene donors such as tert-butylated phosphanylcarboxylic acids and their corresponding aldehydes. These hybrid ambiphilic species that combine Brønsted-acidic and Lewis-basic functional moieties in their structure were characterized by multinuclear NMR and single-crystal X-ray diffraction analys…
Vers une catalyse durable, économe d'atomes et éco-responsable : 0,0001 % de métal, une dose presque homéopathique pour la synthèse pharmaceutique et…
2009
International audience; Comment mettre la chimie en accord avec un développement sociétal durable, harmonieux et respectueux de l'environnement ? Des chimistes de l'Université de Bourgogne cherchent et trouvent des solutions !
CCDC 1877098: Experimental Crystal Structure Determination
2019
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1877102: Experimental Crystal Structure Determination
2019
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1009630: Experimental Crystal Structure Determination
2016
Related Article: Vincent Rampazzi, Julien Roger, Régine Amardeil, Marie-José Penouilh, Philippe Richard, Paul Fleurat-Lessard, and Jean-Cyrille Hierso|2016|Inorg.Chem.|55|10907|doi:10.1021/acs.inorgchem.6b01318
CCDC 1438419: Experimental Crystal Structure Determination
2016
Related Article: Vincent Rampazzi, Julien Roger, Régine Amardeil, Marie-José Penouilh, Philippe Richard, Paul Fleurat-Lessard, and Jean-Cyrille Hierso|2016|Inorg.Chem.|55|10907|doi:10.1021/acs.inorgchem.6b01318
CCDC 1009631: Experimental Crystal Structure Determination
2016
Related Article: Vincent Rampazzi, Julien Roger, Régine Amardeil, Marie-José Penouilh, Philippe Richard, Paul Fleurat-Lessard, and Jean-Cyrille Hierso|2016|Inorg.Chem.|55|10907|doi:10.1021/acs.inorgchem.6b01318
CCDC 1877097: Experimental Crystal Structure Determination
2019
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1877101: Experimental Crystal Structure Determination
2019
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1877094: Experimental Crystal Structure Determination
2019
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1877100: Experimental Crystal Structure Determination
2019
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1438417: Experimental Crystal Structure Determination
2016
Related Article: Vincent Rampazzi, Julien Roger, Régine Amardeil, Marie-José Penouilh, Philippe Richard, Paul Fleurat-Lessard, and Jean-Cyrille Hierso|2016|Inorg.Chem.|55|10907|doi:10.1021/acs.inorgchem.6b01318
CCDC 1009629: Experimental Crystal Structure Determination
2016
Related Article: Vincent Rampazzi, Julien Roger, Régine Amardeil, Marie-José Penouilh, Philippe Richard, Paul Fleurat-Lessard, and Jean-Cyrille Hierso|2016|Inorg.Chem.|55|10907|doi:10.1021/acs.inorgchem.6b01318
CCDC 1877096: Experimental Crystal Structure Determination
2019
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1438418: Experimental Crystal Structure Determination
2016
Related Article: Vincent Rampazzi, Julien Roger, Régine Amardeil, Marie-José Penouilh, Philippe Richard, Paul Fleurat-Lessard, and Jean-Cyrille Hierso|2016|Inorg.Chem.|55|10907|doi:10.1021/acs.inorgchem.6b01318
CCDC 1877099: Experimental Crystal Structure Determination
2019
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1877095: Experimental Crystal Structure Determination
2019
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378