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Accueil > Les équipes > Méthodes et Applications en Chimie Organique (MACO) > Publications

Publications

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2014



  • T. Cañeque, F. M. Truscott, R. Rodriguez, G. Maestri, et M. Malacria, « Electrophilic activation of allenenes and allenynes: analogies and differences between Brønsted and Lewis acid activation », Chemical Society Reviews, vol. 43, nᵒ 9, p. 2916-2926, avr. 2014.
    Résumé : This Tutorial Review summarizes recent examples of electrophilic activation of allenes with particular focus on analogies and differences between Lewis and Brønsted acid activation of these versatile substrates. The aim of this article is to present a general overview of the possibilities offered to chemists using complementary modes of catalysis and to emphasize advantages and limitations of each approach, thereby providing a means to expand the scope of this powerful synthetic methodology.
    Mots-clés : MACO, POLE 1.


  • L. Chenneberg, A. Baralle, M. Daniel, L. Fensterbank, J. - P. Goddard, et C. Ollivier, « Visible Light Photocatalytic Reduction of <i>O</i> -Thiocarbamates: Development of a Tin-Free Barton-McCombie Deoxygenation Reaction », Advanced Synthesis & Catalysis, vol. 356, nᵒ 13, p. 2756-2762, sept. 2014.
    Mots-clés : deoxygenation, electron-transfer, heterocyclic carbene boranes, hydrogen-atom donor, MACO, organic-synthesis, photocatalysis, photoredox catalysis, photoreduction, POLE 1, pschorr reaction, radical deoxygenation, radical reactions, secondary alcohols, synthetic applications, tertiary alcohols, thiocarbamates.
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  • M. Daniel, L. Fensterbank, J. - P. Goddard, et C. Ollivier, « Visible-light photocatalytic oxidation of 1,3-dicarbonyl compounds and carbon–carbon bond formation », Organic Chemistry Frontiers, vol. 1, nᵒ 5, p. 551, 2014.

  • J. L. de la Haye, P. Beaunier, L. Ruhlmann, B. Hasenknopf, E. Lacote, et J. Rieger, « Synthesis of Well-Defined Dawson-TypePoly(N,N-diethylacrylamide) Organopolyoxometalates », ChemPlusChem, vol. 79, nᵒ 2, p. 250-256, févr. 2014.
    Résumé : An organotin-substituted Dawson-type phosphotungstate was covalently linked to a trithiocarbonate group by postfunctionalization methods. This organopolyoxometalate led to a series of polyoxometalate (POM)-poly(N,N-diethylacrylamide) hybrids in a controlled way through reversible addition-fragmentation chain transfer (RAFT) polymerization. Detailed comparison with and without the presence of POMs revealed that they do not profoundly disturb the RAFT mechanism, despite their oxidative power. The molar masses of the polymers were in the range of 10 to 100kgmol(-1) and molar mass dispersities of the composites were low (M-w/M-n<1.5). The POM building block in the hybrids retained the photocatalytic reactivity of the parent Dawson polyanion [P2W18O62](6-). Smaller, more homogeneous, and colloidally more stable silver nanoparticles were formed with the covalently linked POM-polymer compound than with its single unbound components.
    Mots-clés : dawson, GOBS, MACO, metal nanoparticles, optical-properties, organic polymers, organic-inorganic hybrid composites, particles, photocatalysis, photocatalytic reduction, POLE 1, POLE 3, POLE 4, POLYMERES, polymerization, polyoxometalate-polymer hybrid, Polyoxometalates, polyoxotungstates, radical polymerization, radicals, silver nanoparticles.


  • L. Fensterbank et C. Aubert, « Editorial: Max Malacria 65th birthday special issue », Organic Chemistry Frontiers, vol. 1, nᵒ 10, p. 1150-1151, oct. 2014.


  • L. Fensterbank et M. Malacria, « Molecular Complexity from Polyunsaturated Substrates: The Gold Catalysis Approach », Accounts of Chemical Research, vol. 47, nᵒ 3, p. 953-965, mars 2014.
    Mots-clés : bent acyclic allene, c-h bond, cycloisomerization reactions, MACO, mechanistic insights, n-acyl cyanamides, POLE 1, propargylic esters, ptcl2-catalyzed cycloisomerizations, ptcl2-mediated cycloisomerization, rautenstrauch rearrangement, skeletal reorganization.


  • J. Jacquet, E. Salanouve, M. Orio, H. Vezin, S. Blanchard, E. Derat, M. D. - E. Murr, et L. Fensterbank, « Iminosemiquinone radical ligands enable access to a well-defined redox-active CuII–CF3 complex », Chemical Communications, vol. 50, nᵒ 72, p. 10394-10397, août 2014.
    Résumé : The reaction of a copper complex bearing iminosemiquinone ligands with a CF3+ source provides an unprecedented CuII–CF3 complex through ligand-based oxidation. Reactivity of this complex leads to nucleophilic trifluoromethylation of the ligand, suggesting an electronic interplay that results in a formal umpolung of the initial CF3+.
    Mots-clés : E-POM, MACO, POLE 1, POLE 2.
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  • H. Karoui, C. Nsanzumuhire, F. Le Moigne, M. Hardy, D. Siri, E. Derat, A. Rockenbauer, O. Ouari, et P. Tordo, « Synthesis and Spin-Trapping Properties of a Trifluoromethyl Analogue of DMPO: 5-Methyl-5-trifluoromethyl-1-pyrroline N-Oxide (5-TFDMPO) », Chemistry – A European Journal, vol. 20, nᵒ 14, p. 4064-4071, avr. 2014.
    Résumé : The 5-diethoxyphosphonyl-5-methyl-1-pyrroline N-oxide superoxide spin adduct (DEPMPOOOH) is much more persistent (about 15 times) than the 5,5-dimethyl-1-pyrroline N-oxide superoxide spin adduct (DMPOOOH). The diethoxyphosphonyl group is bulkier than the methyl group and its electron-withdrawing effect is much stronger. These two factors could play a role in explaining the different half-lifetimes of DMPOOOH and DEPMPOOOH. The trifluoromethyl and the diethoxyphosphonyl groups show similar electron-withdrawing effects but have different sizes. We have thus synthesized and studied 5-methyl-5-trifluoromethyl-1-pyrroline N-oxide (5-TFDMPO), a new trifluoromethyl analogue of DMPO, to compare its spin-trapping performance with those of DMPO and DEPMPO. 5-TFDMPO was prepared in a five-step sequence by means of the Zn/AcOH reductive cyclization of 5,5,5-trifluoro-4-methyl-4-nitropentanal, and the geometry of the molecule was estimated by using DFT calculations. The spin-trapping properties were investigated both in toluene and in aqueous buffer solutions for oxygen-, sulfur-, and carbon-centered radicals. All the spin adducts exhibit slightly different fluorine hyperfine coupling constants, thereby suggesting a hindered rotation of the trifluoromethyl group, which was confirmed by variable-temperature EPR studies and DFT calculations. In phosphate buffer at pH7.4, the half-life of 5-TFDMPOOOH is about three times shorter than for DEPMPOOOH and five times longer than for DMPOOOH. Our results suggest that the stabilization of the superoxide adducts comes from a delicate balance between steric, electronic, and hydrogen-bonding ef

    fects that involve the group, the hydroperoxyl moiety, and the nitroxide.
    Mots-clés : adducts, depmpo, derivatives, EPR spectroscopy, fluorinated ligands, hydroxyl, in-vitro, MACO, oxygen-centered radicals, phosphorylated nitrone, POLE 1, radicals, reactive oxygen, spin trapping, substituent effects, superoxide, traps.


  • M. Malacria, G. Maestri, P. - A. Deyris, T. Caneque-Cobo, F. Gomes, et V. Narbonne, « Rapid and Convergent Assembly of Natural Benzo[c]phenanthridines by Palladium/Norbornene Catalysis », Heterocycles, vol. 88, nᵒ 1, p. 807, 2014.


  • M. Ménand, S. Adam de Beaumais, L. - M. Chamoreau, E. Derat, S. Blanchard, Y. Zhang, L. Bouteiller, et M. Sollogoub, « Solid-State Hierarchical Cyclodextrin-Based Supramolecular Polymer Constructed by Primary, Secondary, and Tertiary Azido Interactions », Angewandte Chemie International Edition, vol. 53, nᵒ 28, p. 7238-7242, juill. 2014.
    Mots-clés : Azides, cyclodextrins, E-POM, GOBS, inclusion compounds, MACO, POLE 1, POLE 2, POLE 3, POLE 4, POLYMERES, supramolecular polymers.
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  • K. Narasimhan, K. Micoine, E. Lacôte, S. Thorimbert, E. Cheung, B. Hasenknopf, et R. Jauch, « Exploring the utility of organo-polyoxometalate hybrids to inhibit SOX transcription factors », Cell Regeneration, vol. 3, nᵒ 1, p. 10, 2014.


  • V. Narbonne, P. Retailleau, G. Maestri, et M. Malacria, « Diastereoselective Synthesis of Dibenzoazepines through Chelation on Palladium(IV) Intermediates », Organic Letters, vol. 16, nᵒ 2, p. 628-631, janv. 2014.
    Résumé : Joint palladium/norbornene organometallic catalysis allows for straightforward access to dibenzo[c,e]azepines. These synthetically challenging polycyclic frameworks form in one pot via a three-component coupling of an aryl iodide, a bromobenzylamine, and an olefin. A key, atroposelective aryl?aryl coupling from chelated Pd(IV) intermediates dictates the outcome of the cascade. DFT modeling sheds light on the complex mechanism that allows the complete diasteroselectivity to be observed.
    Mots-clés : MACO, POLE 1.


  • F. Nzulu, A. Bontemps, J. Robert, M. Barbazanges, L. Fensterbank, J. - P. Goddard, M. Malacria, C. Ollivier, M. Petit, J. Rieger, et F. Stoffelbach, « Gold-Catalyzed Polymerization Based on Carbene Polycyclopropanation », Macromolecules, vol. 47, nᵒ 19, p. 6652-6656, oct. 2014.
    Résumé : The first polymerization exploiting the carbenic reactivity of homogeneous gold catalysis has been devised. In the presence of a gold catalyst, monomers incorporating both a propargylic ester and an alkene moiety polymerized through a metallocarbene generation/cyclopropanation sequence to afford the corresponding macromolecules. This approach constitutes an unprecedented example of cyclopropanation-based polymerization and allows access to original macromolecule skeletons.
    Mots-clés : MACO, POLE 1, POLE 4, POLYMERES.
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  • M. Petit et J. Monot, « Functionalization of Zirconium Oxide Surfaces », in Chemistry of Organo-Hybrids, B. Charleux, C. Copéret, et E. Lacôte, Éd. John Wiley & Sons, Inc., 2014, p. 168-199.
    Résumé : This chapter gives an overview of the different strategies of functionalizing zirconium oxide surfaces or related materials by highlighting the synthetic approach and the appropriate techniques for the characterization of the modified surface. It focuses on several examples that might be useful to understand the process of functionalization. Two main approaches are reported, one involving the functionalization during the formation of the bulk ceramic, the second is based on the post-functionalization of the surface. The chapter differentiates two categories of analysis, the one giving proof of the functionalization and the other providing information on the morphology of the material. No morphological analysis can be obtained without electron microscopy. Hybrid materials based on zirconia are becoming a great challenge in material chemistry. Indeed, zirconia with its chemical, optical, biological, and mechanical properties has proved to have a large range of application in lots of fields.
    Mots-clés : bulk ceramic, electron microscopy, Hybrid materials, MACO, POLE 1, zirconia, zirconium oxide surfaces.


  • E. Salanouve, G. Bouzemame, S. Blanchard, E. Derat, M. Desage-El Murr, et L. Fensterbank, « Tandem C-H Activation/Arylation Catalyzed by Low-Valent Iron Complexes with Bisiminopyridine Ligands », Chemistry – A European Journal, vol. 20, nᵒ 16, p. 4754-4761, 2014.
    Résumé : Tandem CH activation/arylation between unactivated arenes and aryl halides catalyzed by iron complexes that bear redox-active non-innocent bisiminopyridine ligands is reported. Similar reactions catalyzed by first-row transition metals have been shown to involve substrate-based aryl radicals, whereas our catalytic system likely involves ligand-centered radicals. Preliminary mechanistic investigations based on spectroscopic and reactivity studies, in conjunction with DFT calculations, led us to propose that the reaction could proceed through an inner-sphere CH activation pathway, which is rarely observed in the case of iron complexes. This bielectronic noble-metal-like behavior could be sustained by the redox-active non-innocent bisiminopyridine ligands.
    Mots-clés : aryl halides, bis(imino)pyridine iron, bond activation, catalysis, CH activation, cross-coupling reactions, CH activation, direct arylation, direct functionalization, E-POM, ethylene polymerization catalysts, E_POM, IR spectroscopy, Iron, MACO, POLE 1, POLE 2, POM, redox-active ligands, reductive elimination, unactivated arenes.
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  • F. Schröder, C. Tugny, E. Salanouve, H. Clavier, L. Giordano, D. Moraleda, Y. Gimbert, V. Mouriès-Mansuy, J. - P. Goddard, et L. Fensterbank, « Secondary Phosphine Oxide–Gold(I) Complexes and Their First Application in Catalysis », Organometallics, vol. 33, nᵒ 15, p. 4051-4056, 2014.

    class="resume">Résumé : A series of new secondary phosphine oxide (SPO)–gold(I) complexes have been synthesized and characterized by X-ray crystallography. Complexes exhibited dimeric structures interconnected by O–H···Cl hydrogen bonds. Their first use in homogeneous catalysis is reported and suggests a broad field of application in prototypical enyne cycloisomerization and hydroxy- and methoxycyclization reactions.
    Mots-clés : aryl chlorides, asymmetric hydrogenation, c-n, cationic gold(i) complexes, cross-coupling reactions, cycloisomerization reactions, efficient catalysts, enantioselective synthesis, enynes, Ligands, MACO, POLE 1.
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  • A. Shurki, E. Derat, A. Barrozo, et S. C. L. Kamerlin, « How valence bond theory can help you understand your (bio)chemical reaction », Chemical Society Reviews, oct. 2014.
  • A. Simonneau, G. Maestri, L. Fensterbank, et M. Malacria, « Two-fold tandem acyl-group shift/cyclization via gold catalysis », Arkivoc, p. 287-296, 2014.
    Résumé : A complex cascade involving allendiynes in the presence of a cationic gold catalyst is described. The process features two sequential acyl-group shift/cyclization steps eventually delivering a bicyclic furan derivative from the acyclic precursor. A controlled sequence of molecular events can thus readily deliver the desired heterocycle with a remarkable selectivity.
    Mots-clés : 1,n-enynes, allene, allenic esters, carbocyclization, catalysis, cyclization, Cycloadditions, Cycloisomerization, cycloisomerizations, enynes, Gold, heterocycles, MACO, migration, molecular complexity, POLE 1, transition-metals.

2013



  • J. Agarwal, C. Commandeur, M. Malacria, et S. Thorimbert, « A silicon-position dependent 6-endo-trig cyclization during Tsuji–Trost alkylation », Tetrahedron, vol. 69, nᵒ 45, p. 9398-9405, nov. 2013.
    Résumé : Abstract Two silylated cyclohexenes products have been prepared by using a Tsuji–Trost palladium-catalyzed cyclization. It involves the generation of a cationic π-allylic palladium complex bearing a triethylsilyl group on C-3, which cyclizes via a 6-endo-trig process to afford the cyclohexene derivatives. It is also demonstrated that the position of the silyl group on the starting allylic substrate strongly influenced the reaction. It could favor either the production of the expected cyclohexenyl ring or a diene by an elimination that occurs on the silyl-substituted C-2 π-allylic palladium complex.
    Mots-clés : CHEMBIO, COS, cyclization, Heterocycles, MACO, Palladium, POLE 1, POLE 3, regioselectivity, Silicon derivatives, Tsuji–Trost alkylation.


  • M. Amatore, D. Lebœuf, M. Malacria, V. Gandon, et C. Aubert, « Highly Enantioselective Rhodium-Catalyzed [2+2+2] Cycloaddition of Diynes to Sulfonimines », Journal of the American Chemical Society, vol. 135, nᵒ 12, p. 4576-4579, mars 2013.
    Résumé : A new asymmetric [2+2+2] cycloaddition of diynes to sulfonimines under rhodium catalysis that provides the corresponding enantioenriched 1,2-dihydropyridines in good yields is described.
    Mots-clés : COS, MACO, POLE 1.


  • M. Augé, M. Barbazanges, A. T. Tran, A. Simonneau, P. Elley, H. Amouri, C. Aubert, L. Fensterbank, V. Gandon, M. Malacria, J. Moussa, et C. Ollivier, « Atroposelective [2+2+2] cycloadditions catalyzed by a rhodium(i)–chiral phosphate system », Chemical Communications, vol. 49, nᵒ 71, p. 7833, 2013.


  • A. Baralle, L. Fensterbank, J. - P. Goddard, et C. Ollivier, « Aryl Radical Formation by Copper(I) Photocatalyzed Reduction of Diaryliodonium Salts: NMR Evidence for a CuII/CuI Mechanism », Chemistry – A European Journal, vol. 19, nᵒ 33, p. 10809-10813, 2013.
    Mots-clés : Allylation, copper, iodonium, MACO, photocatalysis, POLE 1, radical reactions.

  • S. Beauviere, F. Brebion, S. Chelli, B. Delouvrie, C. Gomez, O. Kwasnieski, R. M. Mallorquin, F. Najera, G. Vincent, M. R. Vitale, E. Derat, I. Marek, M. Malacria, J. - P. Goddard, et L. Fensterbank, « New Advances in Bis(Sulfoxides) Chemistry », Phosphorus Sulfur and Silicon and the Related Elements, vol. 188, nᵒ 4, p. 367-376, avr. 2013.
    Résumé : The chemistry of bis(sulfoxides) is discussed from two starting materials, (Ss,Ss)-bis-p-tolylsulfinylmethane and (Ss,Ss)-bis-p-tolylsulfinyl alkylidenes. Reactions presented include Michael additions, ionic-radical crossover processes and coordination complexes formations.
    Mots-clés : 1,3-dioxide, acid, asymmetric-synthesis, bis(sulfoxides), bis-sulfoxides, chiral ketene equivalent, complexes, conjugate addition, COS, cycloaddition reactions, ketones, Ligands, MACO, Michael addition, POLE 1, Radical, reactivity.

  • M. M. Brahmi, M. Malacria, D. P. Curran, L. Fensterbank, et E. Lacote, « Substituent Effects in NHC-Boranes: Reactivity Switch in the Nucleophilic Fluorination of NHC-Boranes », Synlett, vol. 24, nᵒ 10, p. 1260-1262, juin 2013.
    Résumé : Substituents on the boron atom of NHC-boranes direct the reactivity of the ligated boreniums obtained through hydride abstraction. Depending on the electronics of the substituent, the reaction is selectively steered toward either B-s

    ubstitution or Lewis base exchange.
    Mots-clés : activation, borenium cation, Boron, boronium, carbene complexes, catalysis, cations, complexes, COS, fluorine, ions, Lewis acids, lewis-acid, MACO, N-heterocyclic carbene, POLE 1.

  • B. Braida, E. Derat, et P. Chaquin, « Theoretical Design of Strong Neutral Radical-Boron Adducts: Trisubstituted Boranes as Potential Radical Scavengers », Chemphyschem, vol. 14, nᵒ 12, p. 2759-2763, août 2013.
    Résumé : The conditions of formation of strong two-center one-electron bonds in neutral compounds are discussed. Both molecular orbital and valence bond analyses show that good candidates are adducts of radicals (.)AR(3) (A=C, Si, Ge) of low ionization energy (IE) with boranes BX3 of high electron affinity (EA). This is confirmed by ab initio calculations. The bond energy of adducts of B(CF3)(3) with various radicals ranges from 18 kcalmol(-1) for (CH3)-C-. to approximately 40 kcalmol(-1) for Me3Si., and a clear correlation with IE-EA difference is found. This allows one to expect B(CF3)(3), among other fluoroboranes, to be an efficient radical scavenger.
    Mots-clés : ab initio calculations, ab-initio, anion, atom, bond energy, boranes, COS, electronegativity, ions, MACO, nuclear-charge, one-electron bond, one-electron bonds, POLE 1, radicals, sigma, spectrum, substituents.

  • E. Derat et G. Maestri, « Understanding palladium complexes structures and reactivities: beyond classical point of view », Wiley Interdisciplinary Reviews-Computational Molecular Science, vol. 3, nᵒ 6, p. 529-541, nov. 2013.
    Résumé : Palladium catalyzed cross-coupling reactions are one of the most widely used class of transformation as shown by the Nobel prize awarded in 2010 to Heck, Negishi, and Suzuki. Computational chemistry has a long-standing partnership with organometallics catalysis, especially with palladium. But even in a largely explored field, novelties can emerge from interplay between experiments and theory. Recent advances grounded on computational chemistry have shown that cooperative effect can explain reactivities; that despite the large number of well-known Pd(0)/Pd(II) catalytic cycle, Pd(IV) is also a realistic intermediate in some cases; that noncovalent interactions can regulate selectivities. So, despite its wide use and recognition, palladium complexes are still full of surprises! (C) 2013 John Wiley & Sons, Ltd.
    Mots-clés : aryl chlorides, arylation, c-c, COS, cross-coupling reaction, density-functional theory, dft, ligand, MACO, oxidative addition, POLE 1, reductive elimination, transmetalation step.

  • S. Donck, A. Baroudi, L. Fensterbank, J. - P. Goddard, et C. Ollivier, « Visible-Light Photocatalytic Reduction of Sulfonium Salts as a Source of Aryl Radicals », Advanced Synthesis & Catalysis, vol. 355, nᵒ 8, p. 1477-1482, mai 2013.
    Résumé : Triarylsulfonium salts are prompted to undergo efficient homolytic reduction by single electron transfer under mild photocatalytic conditions. The liberated aryl radical can then participate in carbon-carbon bond formation processes with allyl sulfones and activated olefins. Triarylsulfonium salts emerge as a valuable and alternative source of aryl radicals for synthesis.
    Mots-clés : arylboronic acids, bond-cleavage, c-h arylation, carbon-carbon bond formation, carbonyl-compounds, COS, diazonium salts, electrochemical reduction, grignard-reagents, MACO, one-electron reduction, onium salts, photocatalysis, photoredox catalysis, POLE 1, radical reactions, reduction, sulfonium salts.


  • J. Dubarle-Offner, M. Barbazanges, M. Augé, C. Desmarets, J. Moussa, M. R. Axet, C. Ollivier, C. Aubert, L. Fensterbank, V. Gandon, M. Malacria, G. Gontard, et H. Amouri, « Gold Compounds Anchored to a Metalated Arene Scaffold: Synthesis, X-ray Molecular Structures, and Cycloisomerization of Enyne », Organometallics, vol. 32, nᵒ 6, p. 1665-1673, mars 2013.
    Résumé : A novel series of π-complexes of phosphino ligands, [Cp*Ru(?6-arene-PAr2)][OTf], has been prepared in which the diarylphosphine unit is attached to a metalated π-arene scaffold. These organometallic phosphino ligands display either an electron-donating methyl group (?PAr2 = ?P(p-tol)2) or electron-withdrawing trifluoromethyl group (?PAr2 = ?P(p-C6H4CF3)2). This unique class of metallo ligands was converted to heterodinuclear gold complexes upon treatment with [AuCl(tht)]. The molecular structures of [Cp*Ru(?6-p-CH3C6H4-P(p-tol)2-Au-Cl)][OTf] and [Cp*Ru(?6-C6H5-P(p-C6H4CF3)2)-Au-Cl][OTf] were ascertained by single-crystal X-ray diffraction. A comparative study of these structures with that of [Cp*Ru(?6-C6H5-PPh2-Au-Cl)][OTf] previously reported revealed important information about the electronic nature of the gold center when it is bonded to a ?PPh2, ?P(p-tol)2, or ?P(p-C6H4CF3)2 metallo ligand. DFT computations also shed light on the effect of [Cp*Ru+] coordination to [AuCl(PAr3)] precatalysts. Several complexes of the family with electron-donating and -withdrawing groups were evaluated toward cycloisomerization reactions of a classical N-tethered 1,6-enyne. These results are presented and discussed.
    Mots-clés : ARC, COS, MACO, POLE 1.


  • D. Gatineau, J. - P. Goddard, V. Mouriès-Mansuy, et L. Fensterbank, « When NHC Ligands Make a Difference in Gold Catalysis », Israel Journal of Chemistry, vol. 53, nᵒ 11-12, p. 892-900, 2013.

  • D. Gatineau, Q. Zhao, D. P. Curran, M. Malacria, E. Lacote, L. Fensterbank, et J. - P. Goddard, « N-Heterocyclic carbene-initiated hydrosilylation of styryl alcohols with dihydrosilanes: a mechanistic investigation », Dalton Transactions, vol. 42, nᵒ 20, p. 7458-7462, 2013.
    Résumé : Investigation of the mechanism of the NHC-initiated hydrosilylation of styryl alcohols in the presence of a dihydrosilane suggests a general base catalysis mechanism and not the activation of the dihydrosilane by the NHC.
    Mots-clés : aldehydes, carbonyl-compounds, COS, cyanosilylation, group-transfer polymerization, ketones, MACO, organocatalytic transfer hydrogenation, POLE 1, reactivity, reduction, ring-opening polymerization, silicon-compounds.

  • Y. Gimbert, L. Fensterbank, V. Gandon, J. - P. Goddard, et D. Lesage, « Ligand Effect in Platinum-Catalyzed Cycloisomerization of 1,6-Enynes: Water or Carbon Monoxide, a Similar Role despite Distinct Electronic Properties? », Organometallics, vol. 32, nᵒ 2, p. 374-376, janv. 2013.
    Résumé : The PtCl2-catalyzed cycloisomerization of 1,6-enynes is considerably accelerated in the presence of carbon monoxide. The effect of CO has been explained by the reinforcement of the electrophilicity of the alkyne moiety once ligated to the pi-acidic [PtCl2(CO)] fragment. However, platinum is also described as wealdy capable of back-donation toward CO. A theoretical study has been carried out to shed light on this apparent contradiction. An alternative explanation based on the approach of CO onto the [PtCl2(eta(4)-(1,6-enyne))] complex is proposed. When CO is ligated to PtCl2, the triple-bond coordination is favored, yet there is no positive influence on the formation of the cyclopropylcarbene key intermediate. The role of CO is actually comparable to that of a water molecule.
    Mots-clés : acetylenes, activation, alkenes, chloro complexes, competition, COS, CSOB, enynes, halides, MACO, palladium(ii), POLE 1, POLE 3, reactivity, skeletal reorganization.


  • M. Guitet, P. Zhang, F. Marcelo, C. Tugny, J. Jiménez-Barbero, O. Buriez, C. Amatore, V. Mouriès-Mansuy, J. - P. Goddard, L. Fensterbank, Y. Zhang, S. Roland, M. Ménand, et M. Sollogoub, « NHC-Capped Cyclodextrins (ICyDs): Insulated Metal Complexes, Commutable Multicoordination Sphere, and Cavity-Dependent Catalysis », Angewandte Chemie International Edition, vol. 52, nᵒ 28, p. 7213–7218, 2013.
    Mots-clés : cavitands, COS, cyclodextrins, Electrochemistry, GOBS, homogeneous catalysis, MACO, N-heterocyclic carbenes, POLE 1, POLE 3.


  • M. - H. Larraufie, M. Malacria, C. Courillon, C. Ollivier, L. Fensterbank, et E. Lacôte, « Synthesis of natural quinazolinones and some of their analogues through radical cascade reactions involving N-acylcyanamides », Tetrahedron, vol. 69, nᵒ 36, p. 7699-7705, sept. 2013.
    Résumé : Abstract Two natural quinazolinones and two analogues can be prepared from the cascade cyclizations of alkyl-substituted N-acylcyanamide radicals, including 5-exo-dig or 6-exo-dig cyclizations onto the cyano group, followed by radical arylations of the resulting amidyl radicals. The fact that one can carry out the cascades from alkyl radicals in addition to aryl, vinyl and aminyl ones, shows the versatility of the method to rapidly access nitrogen-containing polycyclic structures.
    Mots-clés : COS, cyanamides, MACO, POLE 1, Quinazolinones, radical reactions.

  • H. Lenormand, J. - P. Goddard, et L. Fensterbank, « Spirosilane Derivatives as Fluoride Sensors », Organic Letters, vol. 15, nᵒ 4, p. 748-751, févr. 2013.
    Résumé : Spirosilane derivatives have been investigated as fluoride sensors. The reactions between these compounds and different fluoride sources, which resulted In structural alterations, have been monitored and quantified by UV and fluorescence spectroscopy. The high selectivity of these probes for fluoride ions has been demonstrated in either organic or aqueous media.
    Mots-clés : anion recognition, aqueous-media, COS, drinking-water, fluorescent, hypervalent sulfur, MACO, organosilicon compounds, pentaorganosilicates, photophysical properties, POLE 1, selective electrode potentiometry, stabilizing bidentate ligand.


  • G. Maestri, M. Malacria, et E. Derat, « Radical Pd(III)/Pd(I) reductive elimination in palladium sequences », Chemical Communications, vol. 49, nᵒ 88, p. 10424-10426, oct. 2013.
    Résumé : Open-shell mechanisms are often at work in catalytic sequences involving first-row transition metals while usually not considered in palladium chemistry. Herein a computational study suggests their possible relevance in catalytic methods involving paramagnetic Pd(III) intermediates. Indeed C–C bond forming reductive elimination previously thought to occur in Pd(IV) complexes has lower barriers in neutral, radical Pd(III) intermediates instead. These species could form upon addition on Pd(II) of an aryl radical generated via single electron transfer from a photo-active ruthenium complex and have the perfect stereoelectronic arrangement to smoothly undergo the coupling process.
    Mots-clés : c-h arylation, carbon-carbon, catalysis, chemistry, copper, COS, coupling reactions, density functionals, MACO, photocatalysis, pincer complex, POLE 1.


  • M. Malacria et G. Maestri, « Palladium/Norbornene Catalytic System: Chelation as a Tool To Control Regioselectivity of Pd(IV) Reductive Elimination », The Journal of Organic Chemistry, vol. 78, nᵒ 4, p. 1323-1328, 2013.
    Résumé : Palladium/norbornene joint catalysis gives rise to a unique system in which the three most common formal oxidation states of the metal are at work in the same cycle (0, II, and IV). This paper summarizes a selection of synthetic applications and the feasibility of Pd(IV) formation by oxidative addition of aryl halides. On this intermediate, the presence of a suitable chelating group could trigger unexpected aryl–norbornyl coupling, further broadening the scope of readily available polycyclic frameworks.
    Mots-clés : MACO, POLE 1.

  • R. M. Mallorquin, G. Vincent, E. Derat, M. Malacria, J. - P. Goddard, et L. Fensterbank, « New Elements on the Behaviour of a Bissulfinylmethyl Radical », Australian Journal of Chemistry, vol. 66, nᵒ 3, p. 346-353, 2013.
    Résumé : In this article, we have studied the generation of a bissulfinylmethyl radical from the corresponding TEMPO and phenylselenyl bissulfoxide precursors. No univocal formation of the bissulfinylmethyl radical has been observed. Instead, complex mixtures have been obtained in thermal or photochemical conditions, showing prominent C-S homolytic bond cleavage.
    Mots-clés : alkenes, alkoxyamines, alkynes, bis-sulfoxides, COS, MACO, oxidation, POLE 1, thiols.


  • K. Micoine, M. Malacria, E. Lacôte, S. Thorimbert, et B. Hasenknopf, « Regioselective Double Organic Functionalization of Polyoxotungstates through Electrophilic Addition of Aromatic Isocyanates to [P2W17O61(SnR)]7– », European Journal of Inorganic Chemistry, vol. 2013, nᵒ 10-11, p. 1737–1741, 2013.
    Résumé : The direct attachment of several different organic molecules to a single polyoxometalate remains a challenge in the field of functionalized polyoxometalates. In this paper, we show that an organotin-functionalized Dawson-type polyoxotungstate [P2W17O61(SnR)]7– reacts with aromatic isocyanates ArNCO to yield new doubly functionalized compounds [P2W17O61(SnR)(CONHAr)]6–. Both organic moieties, Ar and R, can be varied independently; we have tested nine Ar and three R groups. Therefore, this synthetic methodology represents a way to graft two distinct functional molecules directly onto a polyoxometalate.
    Mots-clés : CHEMBIO, COS, Electrophilic addition, GOBS, Heterocycles, MACO, organic–inorganic hybrid composites, POLE 1, POLE 3, Polyoxometalates, SUPRA, synthesis design, Tungsten.

  • A. Nion, N. Katsonis, A. Marchenko, C. Aubert, et D. Fichou, « Influence of molecular length on the adsorption of linear trimethylsilylacetylene derivatives at the n-tetradecane/Au(111) interface: chemisorption vs. physisorption », New Journal of Chemistry, vol. 37, nᵒ 8, p. 2261-2265, 2013.
    Résumé : Adsorption of two trimethylsilylacetylene (TMSA) derivatives bearing linear alkyl chains of different lengths has been studied at the n-tetradecane/Au(111) interface. The lying or standing orientation of TMSA compounds on the gold surface shows that adsorption is not only controlled by the chemical reactivity of the molecules but also by their size.
    Mots-clés : au(111), COS, FICHOU, Gold, long, MACO, NASCO, organosilane, POLE 1, POLE 2, scanning-tunneling-microscopy, self-assembled monolayers, stm, surfaces.
    Pièce jointe


  • B. Riflade, J. Oble, L. Chenneberg, E. Derat, B. Hasenknopf, E. Lacôte, et S. Thorimbert, « Hybrid polyoxometalate palladacycles: DFT study and application to the Heck reaction », Tetrahedron, vol. 69, nᵒ 27–28, p. 5772-5779, 2013.
    Résumé : The phosphovanadotungstate polyanion [P2W15V3O62]9− is a powerful support to stabilize palladacycles conjugated to the inorganic framework via an organic ligand. The insertion can be directed toward sp2 or sp3 C–H insertion upon appropriate choice of the substitution pattern on the organic ligand. DFT modeling indicates that the strong withdrawing effect of the POM transmitted through the conjugated carbonyl was responsible for this easy insertion. The palladacycles led to the formation of stilbene via a Mizoroki–Heck reaction. However it is likely that the POMs act as Pd-reservoirs for the formation of nanoparticles.
    Mots-clés : catalysis, CHEMBIO, COS, C–H insertion, GOBS, Heck reaction, Heterocycles, Hybrid polyoxometalate, MACO, Palladacycles, POLE 1, POLE 3, SSO, SUPRA.


  • A. Simonneau, Y. Harrak, L. Jeanne-Julien, G. Lemière, V. Mouriès-Mansuy, J. - P. Goddard, M. Malacria, et L. Fensterbank, « Ring Expansions Within the Gold-Catalyzed Cycloisomerization of O-Tethered 1,6-Enynes. Application to the Synthesis of Natural-Product-like Macrocycles », ChemCatChem, vol. 5, nᵒ 5, p. 1096–1099, 2013.
    Mots-clés : COS, Cycloisomerization, enynes, Gold, MACO, POLE 1, radical reactions, ring expansion.


  • A. Simonneau, Y. Harrak, L. Jeanne-Julien, G. Lemière, V. Mouriès-Mansuy, J. - P. Goddard, M. Malacria, et L. Fensterbank, « Inside Cover: Ring Expansions Within the Gold-Catalyzed Cycloisomerization of O-Tethered 1,6-Enynes. Application to the Synthesis of Natural-Product-like Macrocycles (ChemCatChem 5/2013) », ChemCatChem, vol. 5, nᵒ 5, p. 1038–1038, 2013.
    Mots-clés : Cycloisomerization, enynes, Gold, MACO, POLE 1, radical reactions, ring expansion.


  • S. Ventre, E. Derat, M. Amatore, C. Aubert, et M. Petit, « Hydrido-Cobalt Catalyst as a Selective Tool for the Dimerisation of Arylacetylenes: Scope and Theoretical Studies », Advanced Synthesis & Catalysis, vol. 355, nᵒ 13, p. 2584-2590, sept. 2013.


  • S. Ventre, C. Simon, F. Rekhroukh, M. Malacria, M. Amatore, C. Aubert, et M. Petit, « Catalytic Version of Enediyne Cobalt-Mediated Cycloaddition and Selective Access to Unusual Bicyclic Trienes », Chemistry – A European Journal, vol. 19, nᵒ 19, p. 5830–5835, 2013.
    Mots-clés : catalysis, cobalt, COS, cycloaddition, enediynes, MACO, POLE 1, trienes.


  • E. L. Zins, L. Krim, H. Lenormand, J. - P. Goddard, et L. Fensterbank, « Study of Interaction between NO Radicals and Martin’s Spirosilane by Means of IR Spectroscopy », The Journal of Physical Chemistry A, vol. 117, nᵒ 16, p. 3296-3303, 2013.
    Résumé : The matrix isolation method is used to record the IR spectrum of C18H8O2F12Si in the 4000–500 cm–1 range. To gain an IR spectrum with a sufficient resolution, this technique was used with neon as the dilution medium at 5 K. The generated species were characterized by in situ fourier transform infrared (FT-IR) spectroscopy. Once the Martin’s spirosilane 1 (C18H8O2F12Si) was characterized, its reactivity toward NO was investigated under the same experimental conditions (i.e., using neon as a dilution medium at 5 K). In this case, the use of neon at very low temperature leads to the formation of a chemically inert matrix in which the species are trapped and isolated from one another, thus hindering consecutive reactions. As a consequence, intermediates can be observed. This approach allowed us to characterize the NO adduct, leading to the formation of 1-(NO). Concentration effects as well as annealing experiments were carried out. In addition to this experimental approach, products were identified by using reference spectra. Our results proved that, in the dilute phase, the reaction between 1 and NO radicals leads to the formation of an adduct. This stable species can further react with NO to form a more stable compound: 1-(NO)2. This proves the ability of such species to trap NO.
    Mots-clés : MACO, POLE 1.

2012



  • M. Amatore, C. Aubert, M. Malacria, et M. Petit, « Organometallic Complexes of Cobalt (Update 2012) », in Knowledge Updates 2012/3, 1st Editionᵉʳ éd., Thieme Verlag, 2012.
    Résumé : Thieme E-Books & E-Journals
    Mots-clés : cobalt, MACO, POLE 1.


  • A. Baralle, A. Baroudi, M. Daniel, L. Fensterbank, J. - P. Goddard, E. Lacôte, M. - H. Larraufie, G. Maestri, M. Malacria, et C. Ollivier, « Main-Group Elements in Radical Chemistry », in Encyclopedia of Radicals in Chemistry, Biology and Materials, John Wiley & Sons, Ltd, 2012.
    Résumé : This article deals with the radical chemistry of main-group elements, which has been a particularly active field over the last decade. More specifically, we have dealt with the recent synthetic advances involving nitrogen-, oxygen-, phosphorus-, sulfur-, and selenium-centered radicals. Modes of generation of these highly reactive entities have witnessed tremendous developments and their various uses have been treated exhaustively. Mechanistic scenarios have been thoroughly discussed, and stereoselectivity issues, including asymmetric processes, have been addressed. Whenever possible, illustrative applications in the total synthesis of natural products or molecules with relevant properties have been introduced.
    Mots-clés : MACO, nitrogen, Oxygen, phosphorus, POLE 1, Radical, selenium, sulfur.


  • A. Baralle, A. Baroudi, M. Daniel, L. Fensterbank, J. - P. Goddard, E. Lacôte, M. - H. Larraufie, G. Maestri, M. Malacria, et C. Ollivier, « Radical Cascade Reactions », in Encyclopedia of Radicals in Chemistry, Biology and Materials, John Wiley & Sons, Ltd, 2012.
    Résumé : This article deals with the recent developments in radical cascade reactions with a special emphasis on their applications in natural product synthesis. Particular attention has been paid to the mechanisms of the cascade sequences and the involvement of original elementary steps. Section 2 is dedicated to cascades occurring via a purely radical chain mechanism, describing first intramolecular processes, then processes involving both inter- and intramolecular steps. Section 3 is devoted to cascade reactions combining radical and ionic steps. The reactions are classified according to the type of metal reagent used, such as, samarium, titane, manganese, cerium, iron, zinc, silver, and copper. In addition, newer developments in radical cascades triggered by visible light photoredox catalysis are discussed.
    Mots-clés : cascades, cyclizations, fragmentations, homolytic substitutions, MACO, POLE 1, polycyclizations, radical reactions, redox processes, translocations.


  • M. Barbazanges et L. Fensterbank, « Chiral Acyclic Diaminocarbene Complexes: a New Opportunity for Gold Asymmetric Catalysis », ChemCatChem, vol. 4, nᵒ 8, p. 1065–1066, 2012.
    Mots-clés : acyclic diaminocarbene, chirality, COS, cyclization, Gold, homogeneous catalysis, MACO, POLE 1.

  • E. Benedetti, M. Lomazzi, F. Tibiletti, J. - P. Goddard, L. Fensterbank, M. Malacria, G. Palmisano, et A. Penoni, « Synthesis of Nitrogen-Containing Heterocycles via Ring-Closing Ene-Ene and Ene-Yne Metathesis Reactions: An Easy Access to 1-and 2-Benzazepine Scaffolds and Five- and Six-Membered Lactams », Synthesis-Stuttgart, vol. 44, nᵒ 22, p. 3523-3533, nov. 2012.
    Résumé : Novel regioselective ring closing ene-yne metathesis provided an efficient access to different substituted 1-benzazepine scaffolds. The reported synthetic approach could also be used as a powerful tool for the selective formation of a highly functionalizable 2-benzazepine core. This synthetic protocol was even proved to be an efficient way to obtain a functionalizable benzazocine derivative. By modifying the structure of the starting materials, the optimized cyclization finally proved to be a suitable technique to obtain five-and six-membered lactams, enhancing the synthetic application of our method. Five-and six-membered lactams were efficiently prepared by ring-closing metathesis involving the loss of ethylene moiety and affording highly functionalizable compounds showing both electron-withdrawing substituents and electron-donor groups.
    Mots-clés : 1-benzazepine derivatives, aza-claisen rearrangement, benzazepine scaffolds, COS, efficient, enyne-metathesis, Grubbs catalysts, inhibitors, lactams, MACO, natural-product frameworks, nitrogen heterocycles, olefin metathesis, POLE 1, POLE 2, receptor antagonists, regioselective reactions, ring closing ene-ene metathesis, ring closing ene-yne metathesis, solid-phase synthesis, trypanosoma-cruzi.
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