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  • M. Barbazanges, Y. Gimbert, et L. Fensterbank, « Gold-Catalyzed Addition of Propargyl Acetates to Olefins via O-Acyl Migration/Cyclopropanation Sequence: Insight into the Diastereoselective Formation of the Alkene », The Journal of Organic Chemistry, vol. 88, nᵒ 5, p. 3297-3302, mars 2023.
    Résumé : This article discloses a study on the well-known addition of propargyl acetates to olefins via an O-acyl migration/cyclopropanation sequence. Herein, we show that the stereochemical outcome of the olefin is strongly dependent on the gold catalyst and reaction parameters (concentration, temperature, and alkene partner equivalents); the E- and Z-isomers can be selectively formed by the judicious choice of reaction conditions.
    Mots-clés : CSOB, MACO, POLE 1, POLE 3.

  • C. C. Bories, G. Gontard, M. Barbazanges, E. Derat, et M. Petit, « Hydrido-Cobalt Complexes for the Chemo- and Regioselective 1,2-Silylative Dearomatization of N-Heteroarenes », Organic Letters, vol. 25, nᵒ 5, p. 843-848, févr. 2023.
    Résumé : We describe an efficient regio- and chemoselective dearomatization of N-heteroarenes using hydrido-cobalt catalysts. Reactions were performed under mild conditions on a wide range of N-heteroarenes leading exclusively to the silyl-1,2-dihydroheteroarene. Various quinolines and pyridines bearing electron-donating and electron-withdrawing substituents are compatible with this methodology. DFT calculations, NMR spectroscopic studies, and X-ray diffraction analysis underlined the importance of a second silane for the final step of the reaction.
    Mots-clés : MACO, POLE 1.


  • « Boron, silicon, nitrogen and sulfur-based contemporary precursors for the generation of alkyl radicals by single electron transfer and their synthetic utilization - Chemical Society Reviews (RSC Publishing) », 2022. [Online]. Available: [Accessed: 31-janv.-2023].
    Mots-clés : CHEMBIO, MACO, POLE 1, POLE 3.

  • F. Bigi, D. Cauzzi, N. Della Ca’, M. Malacria, R. Maggi, E. Motti, Y. Wang, et G. Maestri, « Evolution of Triangular All-Metal Aromatic Complexes from Bonding Quandaries to Powerful Catalytic Platforms », ACS Organic & Inorganic Au, vol. 2, nᵒ 5, p. 373-385, oct. 2022.
    Résumé : This manuscript describes an overview on the literature detailing the observation of trinuclear complexes that present delocalized metal–metal bonds similar to those of regular aromatics, which are formed combining main group elements. A particular emphasis is given to the structural and electronic features of aromatic clusters that are sufficiently stable to allow their isolation. In parallel to the description of their key bonding properties, the work presents reported catalytic applications of these complexes, which already span from elaborated C–C-forming cascades to highly efficient cross-coupling methods. These examples present peculiar aspects of the unique reactivity exerted by all-metal aromatic complexes, which can often be superior to their established, popular mononuclear peers in terms of chemoselectivity and chemical robustness.
    Mots-clés : MACO, POLE 1.

  • F. Célerse, T. J. Inizan, L. Lagardère, O. Adjoua, P. Monmarché, Y. Miao, E. Derat, et J. - P. Piquemal, « An Efficient Gaussian-Accelerated Molecular Dynamics (GaMD) Multilevel Enhanced Sampling Strategy: Application to Polarizable Force Fields Simulations of Large Biological Systems », Journal of Chemical Theory and Computation, vol. 18, nᵒ 2, p. 968-977, févr. 2022.
    Résumé : We introduce a novel multilevel enhanced sampling strategy grounded on Gaussian-accelerated Molecular Dynamics (GaMD). First, we propose a GaMD multi-GPUs-accelerated implementation within the Tinker-HP molecular dynamics package. We introduce the new “dual-water” mode and its use with the flexible AMOEBA polarizable force field. By adding harmonic boosts to the water stretching and bonding terms, it accelerates the solvent–solute interactions while enabling speedups, thanks to the use of fast multiple–time step integrators. To further reduce the time-to-solution, we couple GaMD to Umbrella Sampling (US). The GaMD─US/dual-water approach is tested on the 1D Potential of Mean Force (PMF) of the solvated CD2–CD58 system (168 000 atoms), allowing the AMOEBA PMF to converge within 1 kcal/mol of the experimental value. Finally, Adaptive Sampling (AS) is added, enabling AS–GaMD capabilities but also the introduction of the new Adaptive Sampling–US–GaMD (ASUS–GaMD) scheme. The highly parallel ASUS–GaMD setup decreases time to convergence by, respectively, 10 and 20 times, compared to GaMD–US and US. Overall, beside the acceleration of PMF computations, Tinker-HP now allows for the simultaneous use of Adaptive Sampling and GaMD-”dual water” enhanced sampling approaches increasing the applicability of polarizable force fields to large-scale simulations of biological systems.
    Mots-clés : MACO, POLE 1.

  • V. Corcé, C. Ollivier, et L. Fensterbank, « Boron, silicon, nitrogen and sulfur-based contemporary precursors for the generation of alkyl radicals by single electron transfer and their synthetic utilization », Chemical Society Reviews, vol. 51, nᵒ 4, p. 1470-1510, févr. 2022.
    Résumé : Recent developments in the use of boron, silicon, nitrogen and sulfur derivatives in single-electron transfer reactions for the generation of alkyl radicals are described. Photoredox catalyzed, electrochemistry promoted or thermally-induced oxidative and reductive processes are discussed highlighting their synthetic scope and discussing their mechanistic pathways.
    Mots-clés : CHEMBIO, MACO, POLE 1, POLE 3.

  • T. Deis, J. Forte, L. Fensterbank, et G. Lemière, « Synthesis and Reactivity of Martin’s Spirosilane-Derived Chloromethylsilicate », Molecules, vol. 27, nᵒ 6, p. 1767, janv. 2022.
    Résumé : Pentacoordinate silicon derivatives with a chloromethyl ligand are versatile compounds that are usually obtained from the corresponding tetravalent trialkoxy- or trihalogeno(chloromethyl)silane. We describe herein the synthesis of a chloromethylsilicate bearing two Martin’s ligands readily obtained by addition of in situ generated chloromethyllithium to a spirosilane. The reactivity of this new species was evaluated and it has been established that the chloride is displaced by strong nucleophiles such as alkyllithiums and (hetero)aryllithiums. In Lewis acidic conditions, the pentacoordinate silicon species rearranges through a formal insertion of a methylene into one Si–C bond, to form a new tetravalent spirosilane with a six-membered ring. The same kind of rearrangement can be triggered also by addition of a Lewis base. The mechanism of the rearrangement in both conditions has been studied by means of DFT calculations.
    Mots-clés : DFT calculations, MACO, pentacoordination, POLE 1, Sila-Matteson rearrangement, silicon, spirosilane.

  • T. Deis, J. Maury, F. Medici, M. Jean, J. Forte, N. Vanthuyne, L. Fensterbank, et G. Lemière, « Synthesis and Optical Resolution of Configurationally Stable Zwitterionic Pentacoordinate Silicon Derivatives », Angewandte Chemie International Edition, vol. 61, nᵒ 3, p. e202113836, 2022.
    Résumé : Stereogenic silicon centres in functionalised tetracoordinated organosilanes generally exhibit very high configurational stability under neutral conditions. This stability drops completely when higher coordination states of the silicon centre are reached due to rapid substituent exchange. Herein we describe the synthesis of chiral and neutral pentacoordinate silicon derivatives with high configurational stability. The zwitterionic nature of these air- and water-tolerant species allows for the first time their direct and efficient optical resolution using chiral HPLC techniques. By means of this method, pentacoordinate silicon compounds exhibiting high Si-inversion have been obtained as single enantiomers. A rationalisation of the enantiomerisation pathways has been also carried out using DFT calculations.
    Mots-clés : Chiral HPLC, Chirality, MACO, Optical resolution, POLE 1, Silicon, Zwitterion.

  • A. Millanvois, C. Ollivier, et L. Fensterbank, « Bis(catecholato)silicates: Synthesis and Structural Data », European Journal of Inorganic Chemistry, vol. 2022, nᵒ 17, p. e202101109, 2022.
    Résumé : This minireview provides an overview of the synthesized bis(catecholato)silicates based on the nature of the alkyl or aryl residues and associated cations as well as the methods developed for this purpose. Structural and analytical data such as the 29Si NMR shift of silicon penta- and hexacoordinate derivatives, selected examples of crystal structures by X-ray diffraction analysis and oxidation potentials of silicates are reported. Some aspects of reactivity are also mentioned.
    Mots-clés : Bis(catecholo)silicate, Hypercoordinated silicon, MACO, Oxidation potential, POLE 1, Silicon NMR, X-ray analysis.

  • O. Sadek, M. Abdellaoui, A. Millanvois, C. Ollivier, et L. Fensterbank, « Organometallic catalysis under visible light activation: benefits and preliminary rationales », Photochemical & photobiological sciences, vol. 21, nᵒ 4, p. 585-606, avr. 2022.
    Résumé : Organometallic catalysis under visible light activation is an emerging field. Activation by photosensitization or by direct light absorption of organometallic complexes can facilitate or trigger elementary steps in a catalytic cycle such as pre-catalyst reduction, oxidative addition, transmetalation and reductive elimination, as well as the ability of generating radical intermediates, widening the structural diversity offered by classical couplings. This perspective aims to highlight key examples of these light-induced or enhanced processes, with an emphasis on the underlying mechanisms involved.
    Mots-clés : MACO, POLE 1.

  • T. E. Schirmer, M. Abdellaoui, A. Savateev, C. Ollivier, M. Antonietti, L. Fensterbank, et B. König, « Mesoporous Graphitic Carbon Nitride as a Heterogeneous Organic Photocatalyst in the Dual Catalytic Arylation of Alkyl Bis(catecholato)silicates », Organic Letters, vol. 24, nᵒ 13, p. 2483-2487, avr. 2022.
    Résumé : Mesoporous graphitic carbon nitride (mpg-CN) is introduced as a heterogeneous photocatalyst to perform dual photoredox- and nickel-catalyzed cross-coupling reactions between alkyl bis(catecholato)silicates as radical precursors and aryl or alkenyl bromides. The synergy between this recyclable photocatalyst and the broadly applied homogeneous nickel complex [Ni(dtbbpy)Br2] gives access to C(sp2)–C(sp3) cross-coupling products in a sustainable fashion. The recycled mpg-CN photocatalyst was analyzed by time-resolved emission spectroscopy and EPR spectroscopy.
    Mots-clés : MACO, POLE 1.

  • A. Serafino, M. Chiminelli, D. Balestri, L. Marchiò, F. Bigi, R. -mondo Maggi, M. Malacria, et G. Maestri, « Dimerizing cascades of enallenamides reveal the visible-light-promoted activation of cumulated C–C double bonds », Chemical Science, vol. 13, nᵒ 9, p. 2632-2639, 2022.

  • X. Wang, L. Sun, M. Wang, G. Maestri, M. Malacria, X. Liu, Y. Wang, et L. Wu, « C−I Selective Sonogashira and Heck Coupling Reactions Catalyzed by Aromatic Triangular Tri-palladium », European Journal of Organic Chemistry, vol. 2022, nᵒ 10, p. e202200009, 2022.
    Résumé : Aromatic triangular tri-palladium cations 1–3, abbreviated as [Pd3]+, have shown interesting photoelectric properties, Lewis basic character, and excellent activities in catalytic hydrogenation. Herein, we report the highly efficient and C−I selective Sonogashira and Heck coupling reactions catalyzed by these tri-palladium complexes. Benefiting from the moderate C−I bond association energy, these tri-palladiums presented exclusive reactivities to aryl iodides over the brominated aromatics in coupling reactions. In the Sonogashira pathway, good to excellent isolated yields (71–95 %) were achieved. Gram-scale reaction reached 93 % of yield with palladium loading as few as 0.06 mol %. We also explored the electronic and steric effects for phenyl alkynes and aryl iodides including heteroaromatics like thiophene, pyridine, pyrazole, and pyrazine. Similarly, yields of 71–96 % were obtained for palladium loading of 1.5 mol% through catalyzed Heck coupling of aryl iodides and alkenes. The HRMS monitoring revealed that [Pd3]+ maintained as whole entity during the catalytic process due to its robusness.
    Mots-clés : All-metal aromaticity, C−I selective, Heck coupling, MACO, POLE 1, Sonogashira coupling, Triangular palladium complexes.

  • F. Zhao, M. Abdellaoui, W. Hagui, M. Ballarin-Marion, J. Berthet, V. Corcé, S. Delbaere, H. Dossmann, A. Espagne, J. Forté, L. Jullien, T. Le Saux, V. Mouriès-Mansuy, C. Ollivier, et L. Fensterbank, « Reactant-induced photoactivation of in situ generated organogold intermediates leading to alkynylated indoles via Csp2-Csp cross-coupling », Nature Communications, vol. 13, nᵒ 1, p. 2295, avr. 2022.
    Résumé : Photosensitization of organogold intermediates is an emerging field in catalysis. In this context, an access to 2,3-disubstituted indoles from o-alkynyl aniline and iodoalkyne derivatives via a gold-catalyzed sequence under visible-light irradiation and in the absence of an exogenous photocatalyst was uncovered. A wide scope of the process is observed. Of note, 2-iodo-ynamides can be used as electrophiles in this cross-coupling reaction. The resulting N-alkynyl indoles lend themselves to post-functionalization affording valuable scaffolds, notably benzo[a]carbazoles. Mechanistic studies converge on the fact that a potassium sulfonyl amide generates emissive aggregates in the reaction medium. Static quenching of these aggregates by a vinylgold(I) intermediate yields to an excited state of the latter, which can react with an electrophile via oxidative addition and reductive elimination to forge the key C-C bond. This reactant-induced photoactivation of an organogold intermediate opens rich perspectives in the field of cross-coupling reactions.
    Mots-clés : CHEMBIO, CSOB, MACO, Photocatalysis, POLE 1, POLE 3, Reaction mechanisms.

  • F. Zhao, W. Hagui, M. Ballarín-Marión, C. Ollivier, V. Mouriès-Mansuy, et L. Fensterbank, « 3-Sulfonylindoles via Gold- or Silver-Catalyzed Cyclization─1,3-Sulfonyl Migration Sequences under Visible Light Irradiation », ACS Organic & Inorganic Au, sept. 2022.
    Résumé : A pathway for the synthesis of 3-sulfonylindoles has been devised. Upon blue LED irradiation, in the presence of a gold(I) or a silver(I) salt, ortho-alkynyl N-sulfonyl precursors readily undergo a 5-endo-dig cyclization concomitant with a 1,3-sulfonyl migration. While the gold-catalyzed reaction takes place in photocatalyst-free conditions, an iridium photocatalyst (Ir[dF(CF3)ppy]2(dtbbpy)PF6) is necessary with silver catalysis. Mechanistic studies featuring the generation of a sulfonyl radical support this dichotomy.
    Mots-clés : MACO, POLE 1.


  • F. Bigi, G. Cera, R. Maggi, Y. Wang, M. Malacria, et G. Maestri, « Is Aromaticity a Driving Force in Catalytic Cycles? A Case from the Cycloisomerization of Enynes Catalyzed by All-Metal Aromatic Pd3+ Clusters and Carboxylic Acids », The Journal of Physical Chemistry A, vol. 125, nᵒ 46, p. 10035-10043, nov. 2021.
    Résumé : The work details a mechanistic study based on density functional theory modeling on the cycloisomerization of polyunsaturated substrates catalyzed by all-metal aromatic tripalladium complexes and carboxylic acids. These clusters are an emerging class of catalysts for a variety of relevant transformations, including C–C forming processes that occur under mild conditions and display synthetic features complementary to those of established mononuclear complexes. This study is the first computational one devoted to the comprehension of the series of elementary steps involved in a synthetic transformation catalyzed by an all-metal aromatic complex. Present results confirm previous experimental hints on the striking mechanistic differences exerted by these clusters with respect to the usual cyclization pathways of related substrates. Moreover, the catalytic cycle involving present all-metal aromatic clusters closely parallels the mechanism of the aromatic substitution of regular arenes.
    Mots-clés : MACO, POLE 1.

  • L. Fensterbank et C. Ollivier, Introduction: Radicals, from Gomberg to Planet Mars, 1st editionᵉʳ éd. Thieme Verlag, 2021.
    Résumé : Thieme E-Books & E-Journals
    Mots-clés : MACO, POLE 1.

  • L. Fensterbank, C. Ollivier, A. Roblin, et M. Barbazanges, « Chiral Counterions in Enantioselective Organometallic Catalysis », in Topics in Enantioselective Catalysis, vol. Volume 9, WORLD SCIENTIFIC, 2021, p. 95-122.

  • E. Levernier, K. Jaouadi, H. - R. Zhang, V. Corcé, A. Bernard, G. Gontard, C. Troufflard, L. Grimaud, E. Derat, C. Ollivier, et L. Fensterbank, « Phenyl Silicates with Substituted Catecholate Ligands: Synthesis, Structural Studies and Reactivity », Chemistry – A European Journal, vol. 27, nᵒ 34, p. 8782-8790, 2021.
    Résumé : While the generation of aryl radicals by photoredox catalysis under reductive conditions is well documented, it has remained challenging under an oxidative pathway. Because of the easy photo-oxidation of alkyl bis-catecholato silicates, a general study of phenyl silicates bearing substituted catecholate ligands has been achieved. The newly synthesized phenyl silicates have been fully characterized, and their reactivity has been explored. It was found that, thanks to the substitution of the catecholate moiety, notably with the 4-cyanocatecholato ligand, the phenyl radical could be generated and trapped. Computational studies provided a rationale for these findings.
    Mots-clés : aryl radicals, CHEMBIO, MACO, oxidation, photoredox catalysis, POLE 1, POLE 3, silicates.

  • X. Li, J. Li, X. Wang, L. Wu, Y. Wang, G. Maestri, M. Malacria, et X. Liu, « Photoelectric properties of aromatic triangular tri-palladium complexes and their catalytic applications in the Suzuki–Miyaura coupling reaction », Dalton Transactions, vol. 50, nᵒ 34, p. 11834-11842, août 2021.
    Résumé : The photoelectric properties and catalytic activities of substituted triphenylphosphine and sulfur/selenium ligand supported aromatic triangular tri-palladium complexes 1–4, abbreviated as [Pd3]+, were investigated. The cyclic voltammogram of [Pd3]+ in CH3CN-nBu4NPF6 showed a single quasi-reversible wave which was consistent with their robust property and provided preliminary proof for their electron transfer processes in catalysis. With excitation at 267 nm, [Pd3]+ exhibited strong ratiometric fluorescence at 550 and 780 nm at a temperature gradient from 77 K to 287 K. These peculiar triangular tri-palladium complexes showed excellent catalytic activities and exclusive reactivity with aryl iodides over the other halogenated aromatics in the Suzuki–Miyaura coupling reaction. The electronic and steric hindrance effects of substituents on the aryl iodides and aryl boronic acids including heteroaromatics like pyridine, pyrazine and thiophenes were explored and most substrates achieved up to 99% of yields. (2-[1,1′-Biphenyl]-2-ylbenzothiazole) which was analogous to the selective cyclooxygenase-2 (COX-2) inhibitors was also synthesized with our tri-palladium catalyst and gave good isolated yield (94%). The study of the catalytic process revealed that the mechanism of the reaction may involve the replacement of the sulphur ligand on [Pd3]+ by iodine from aryl iodides, which was beneficial for the matching of C–I bond energy.
    Mots-clés : MACO, POLE 1.

  • B. Neil, F. Lucien, L. Fensterbank, et C. Chauvier, « Transition-Metal-Free Silylation of Unactivated C(sp2)–H Bonds with tert-Butyl-Substituted Silyldiazenes », ACS Catalysis, vol. 11, nᵒ 21, p. 13085-13090, nov. 2021.
    Résumé : Aromatic organosilanes bearing C(sp2)–Si bonds have found increasing applications across the chemical science, yet are mostly produced by atom-uneconomical stoichiometric procedures. Catalytic alternatives using hydrosilanes as silicon sources have also been described, but they display unfavorable thermodynamics and are mostly based on expensive catalytic systems, often derived from noble metals, or lack generality. Herein, we describe the use of an alternative silicon source, namely the tert-butyl-substituted silyldiazenes (tBu–N═N–SiR3), that are readily accessible from commercially available precursors and whose structure enables the C(sp2)–H bond silylation of unactivated heteroaryl and aryl compounds under ambient, transition-metal-free catalytic conditions.
    Mots-clés : MACO, POLE 1.


  • A. Cartier, E. Levernier, A. - L. Dhimane, T. Fukuyama, C. Ollivier, I. Ryu, et L. Fensterbank, « Synthesis of Aliphatic Amides through a Photoredox Catalyzed Radical Carbonylation Involving Organosilicates as Alkyl Radical Precursors », Advanced Synthesis & Catalysis, vol. 362, nᵒ 11, p. 2254-2259, 2020.
    Résumé : Alkyl radicals, from primary to tertiary, formed by photocatalyzed oxidation of organosilicates, are involved efficiently in radical carbonylation with carbon monoxide (CO), in the presence of various amines and CCl4, leading to a variety of amides in moderate to good yields.
    Mots-clés : Carbonylation, MACO, multi-component reaction, photooxidative catalysis, POLE 1, radical/polar, silicates.

  • Y. Ren, J. Forte, K. Cheaib, N. Vanthuyne, L. Fensterbank, H. Vezin, M. Orio, S. Blanchard, et M. Desage-El Murr, « Optimizing Group Transfer Catalysis by Copper Complex with Redox-Active Ligand in an Entatic State », Iscience, vol. 23, nᵒ 3, p. UNSP 100955, mars 2020.
    Résumé : Metalloenzymes use earth-abundant non-noble metals to perform high-fidelity transformations in the biological world. To ensure chemical efficiency, metalloenzymes have acquired evolutionary reactivity-enhancing tools. Among these, the entatic state model states that a strongly distorted geometry induced by ligands around a metal center gives rise to an energized structure called entatic state, strongly improving the reactivity. However, the original definition refers both to the transfer of electrons or chemical groups, whereas the chemical application of this concept in synthetic systems has mostly focused on electron transfer, therefore eluding chemical transformations. Here we report that a highly strained redox-active ligand enables a copper complex to perform catalytic nitrogen- and carbon-group transfer in as fast as 2 min, thus exhibiting a strong increase in reactivity compared with its unstrained analogue. This report combines two reactivity-enhancing features from metalloenzymes, entasis and redox cofactors, applied to group-transfer catalysis.
    Mots-clés : aziridination, cu, E-POM, galactose-oxidase, generation, MACO, metal-complexes, models, oxidation, POLE 1, POLE 2, radicals, reactivity, site.

  • A. Serafino, D. Balestri, L. Marchiò, M. Malacria, E. Derat, et G. Maestri, « Orthogonal Syntheses of 3.2.0 Bicycles from Enallenes Promoted by Visible Light », Organic Letters, vol. 22, nᵒ 16, p. 6354-6359, août 2020.
    Résumé : Enallenes can be readily converted into two families of 3.2.0 (hetero)bicycles with high diastereoselectivities through the combination of visible light with a suitable Ir(III) complex (1 mol %). Two complementary pathways, namely, a photocycloaddition versus a radical chain, can then take place. Both manifolds grant complete regiocontrol of the allene difunctionalization. This is accompanied by an original 1,3-group shift using sulfonyl a

    llenamides that deliver a congested tetrasubstituted headbridging carbon in the corresponding product.
    Mots-clés : MACO, POLE 1.


  • C. Cecchini, G. Cera, M. Lanzi, L. Marchiò, M. Malacria, et G. Maestri, « Diastereoselective bicyclization of enynols via gold catalysis », Organic Chemistry Frontiers, vol. 6, nᵒ 20, p. 3584-3588, oct. 2019.
    Résumé : A Au(I)-catalyzed protocol for the cycloisomerizations of enynols into 4.3.0 (hetero)bicycles with complete regio- and diastereoselection is herein described. The sequential bicyclization exploits substrates with a styryl arm, disclosing in turn a reactive pathway that is complementary to the literature reports. The use of a gold(I)–phosphite catalyst allowed for the synthesis of functionalized polycycles under mild conditions, with good yields and low catalyst loadings (1 mol%).
    Mots-clés : MACO, POLE 1.

  • C. Cecchini, M. Lanzi, G. Cera, M. Malacria, et G. Maestri, « Complementary Reactivity of 1,6-Enynes with All-Metal Aromatic Trinuclear Complexes and Carboxylic Acids », Synthesis, vol. 51, nᵒ 5, p. 1216-1224, mars 2019.
    Résumé : The distinct reactivity of 1,6-enynes in the presence of a trinuclear metal complex activated by a carboxylic acid is presented. The triplatinum catalyst enables the cyclization of the substrate and subsequent incorporation of a nucleophile in the final product. In contrast, sequential cyclization/double bond shift occurs under analogous conditions in the presence of the corresponding tripalladium complex.
    Mots-clés : aromaticity, clusters, cyclization, Key words enynes, MACO, palladium, platinum, POLE 1.

  • V. Corcé, C. Lévêque, C. Ollivier, et L. Fensterbank, « 15 Silicates in Photocatalysis », in Photocatalysis in Organic Synthesis, 1st editionᵉʳ éd., Thieme Verlag, 2019.
    Résumé : Bis(catecholato)silicates have emerged as robust alkyl radical sources under photocatalysis. This chapter describes the preparation of various silicates and their utilization under photocatalytic conditions for the formation of C–C and C–O bonds. The last section focuses on the use of silicates in photoredox/nickel dual catalysis.
    Mots-clés : CHEMBIO, MACO, POLE 3.

  • J. Jacquet, L. Fensterbank, et M. Desage-El Murr, « Trifluoromethylation and Related Reactions », in Non-Noble Metal Catalysis, John Wiley & Sons, Ltd, 2019, p. 329-354.
    Résumé : Among the ever-increasing variety of transformations catalyzed by earth-abundant metals, introduction of fluorine-containing groups is at the forefront of current synthetic interests. The resulting products find widespread applications from agrochemicals to pharmaceuticals, and this versatility plays no mean part in the wealth of methods that are currently being developed. The most recent contributions to this fast-paced field are presented hereafter and should provide the reader with an overview of the latest developments.
    Mots-clés : copper, MACO, nickel, perfluoroalkylation, POLE 1, trifluoromethylation, trifluoromethylthiolation.

  • M. Lanzi, V. Santacroce, D. Balestri, L. Marchiò, F. Bigi, R. Maggi, M. Malacria, et G. Maestri, « Visible-Light-Promoted Polycyclizations of Dienynes », Angewandte Chemie International Edition, vol. 58, nᵒ 20, p. 6703-6707, 2019.
    Résumé : A variety of linear dienynes can deliver complex tetracyclic frameworks in the presence of an IrIII complex and visible light. Product formation involves the generation of four new C−C bonds and six contiguous stereocenters, which decorate two [3.1.0] bicyclic units tethered through their bridging quaternary carbon atoms. The internal alkyne acts as a formal dicarbenoid for the generation of two cyclopropanes in these radical cation cascades. This behavior has not been previously observed for organic reactive intermediates and can be extended to intermolecular reactions and diendiynes.
    Mots-clés : carbenoids, domino reactions, MACO, photocatalysis, POLE 1, radical cations, visible light.


  • « N-Heterocyclic carbene-stabilized gold nanoparticles with tunable sizes - Dalton Transactions (RSC Publishing) », Dalton Transactions, 2018. [Online]. Available: [Accessed: 31-janv.-2023].

  • G. Cera, M. Lanzi, D. Balestri, N. Della Ca’, R. Maggi, F. Bigi, M. Malacria, et G. Maestri, « Synthesis of Carbolines via Palladium/Carboxylic Acid Joint Catalysis », Organic Letters, vol. 20, nᵒ 11, p. 3220-3224, juin 2018.
    Résumé : The combination of a Pd(0) complex with benzoic acid converts propargylic tryptamines to the corresponding tetrahydro-β-carbolines. The method uses unprotected indoles and affords the desired products with ample functional group tolerance. Detailed modeling studies reveal a close synergy between the organic and metal catalysts, which enables sequential alkyne isomerization, indole C–H activation, and eventual C–C reductive elimination to afford the target heterocycles.
    Mots-clés : MACO, POLE 1.

  • G. Cera, M. Lanzi, F. Bigi, R. Maggi, M. Malacria, et G. Maestri, « Bi-directional alkyne tandem isomerization via Pd(0)/carboxylic acid joint catalysis: expedient access to 1,3-dienes », Chemical Communications, vol. 54, nᵒ 99, p. 14021-14024, déc. 2018.
    Résumé : An in situ formed palladium hydride catalyst enables the sequential dual isomerization of propargylamide derivatives to 1-amido-1,3-dienes with high chemo- and regioselectivity. The reaction shows ample functional group tolerance, delivering a valuable class of products, including highly deuterated ones, from readily available reagents. The reaction occurs through a complex mechanism studied by DFT modelling.
    Mots-clés : MACO, POLE 1.

  • M. Lanzi, T. Cañeque, L. Marchiò, R. Maggi, F. Bigi, M. Malacria, et G. Maestri, « Alternative Routes to Tricyclic Cyclohexenes with Trinuclear Palladium Complexes », ACS Catalysis, vol. 8, nᵒ 1, p. 144-147, janv. 2018.
    Résumé : Highly symmetric all-metal aromatic Pd3+ complexes can catalyze the cycloisomerization of terminal 1,6-enynes and internal dienynes under mild conditions. Modification of substrates dictates the mechanism and steers the reaction toward different polycyclic frameworks, enabling the development of comple

    x cascades. The reactivity of Pd(4/3) complexes is complementary to that of mononuclear Pd(0) and Pd(II) ones.
    Mots-clés : MACO, POLE 1.

  • H. Patel, M. Periyasamy, G. P. Sava, A. Bondke, B. W. Slafer, S. H. B. Kroll, M. Barbazanges, R. Starkey, S. Ottaviani, A. Harrod, E. O. Aboagye, L. Buluwela, M. J. Fuchter, A. G. M. Barrett, R. C. Coombes, et S. Ali, « ICEC0942, an Orally Bioavailable Selective Inhibitor of CDK7 for Cancer Treatment », Molecular Cancer Therapeutics, vol. 17, nᵒ 6, p. 1156-1166, mai 2018.
    Résumé : Recent reports indicate that some cancer types are especially sensitive to transcription inhibition, suggesting that targeting the transcriptional machinery provides new approaches to cancer treatment. Cyclin-dependent kinase (CDK)7 is necessary for transcription, and acts by phosphorylating the C-terminal domain (CTD) of RNA polymerase II (PolII) to enable transcription initiation. CDK7 additionally regulates the activities of a number of transcription factors, including estrogen receptor (ER)-α. Here we describe a new, orally bioavailable CDK7 inhibitor, ICEC0942. It selectively inhibits CDK7, with an IC50 of 40 nmol/L; IC50 values for CDK1, CDK2, CDK5, and CDK9 were 45-, 15-, 230-, and 30-fold higher. In vitro studies show that a wide range of cancer types are sensitive to CDK7 inhibition with GI50 values ranging between 0.2 and 0.3 μmol/L. In xenografts of both breast and colorectal cancers, the drug has substantial antitumor effects. In addition, combination therapy with tamoxifen showed complete growth arrest of ER-positive tumor xenografts. Our findings reveal that CDK7 inhibition provides a new approach, especially for ER-positive breast cancer and identify ICEC0942 as a prototype drug with potential utility as a single agent or in combination with hormone therapies for breast cancer. ICEC0942 may also be effective in other cancers that display characteristics of transcription factor addiction, such as acute leukaemia and small-cell lung cancer. Mol Cancer Ther; 17(6); 1156–66. ©2018 AACR.
    Mots-clés : MACO, POLE 1.


  • Q. Arnoux, A. Boucly, V. Barth, R. Benbalagh, A. Cossaro, L. Floreano, M. Silly, F. Sirotti, E. Derat, S. Carniato, F. Bournel, J. - J. Gallet, D. Fichou, L. Tortech, et F. Rochet, « Energy-Level Alignment of a Hole-Transport Organic Layer and ITO: Toward Applications for Organic Electronic Devices », ACS Applied Materials & Interfaces, vol. 9, nᵒ 36, p. 30992-31004, sept. 2017.
    Résumé : 2,2′,6,6′-Tetraphenyl-4,4′-dipyranylidene (DIPO-Ph4) was grown by vacuum deposition on an indium tin oxide (ITO) substrate. The films were characterized by atomic force microscopy as well as synchrotron radiation UV and X-ray photoelectron spectroscopy to gain an insight into the material growth and to better understand the electronic properties of the ITO/DIPO-Ph4 interface. To interpret our spectroscopic data, we consider the formation of cationic DIPO-Ph4 at the ITO interface owing to a charge transfer from the organic layer to the substrate. Ionization energy DFT calculations of the neutral and cationic species substantiate this hypothesis. Finally, we present the energetic diagram of the ITO/DIPO-Ph4 system, and we discuss the application of this interface in various technologically relevant systems, as a hole-injector in OLEDs or as a hole-collector interfacial layer adjacent to the prototypical OPV layer P3HT:PCBM.
    Mots-clés : E-POM, MACO, POLE 1, POLE 2.

  • T. Cañeque, F. Gomes, T. T. Mai, F. Blanchard, P. Retailleau, J. - F. Gallard, G. Maestri, M. Malacria, et R. Rodriguez, « A Synthetic Study towards the Marmycins and Analogues », Synthesis, vol. 49, nᵒ 3, p. 587-592, févr. 2017.
    Résumé : A methodological study towards the total synthesis of marmycin A/B is described exploiting a commercial anthraquinone molecule as model compound. The challenging synthetic pathway uncovers a copper-catalysed Ullmann cross-coupling to attach the sugar backbone by means of C–N bond formation and, finally, an intramolecular Friedel–Crafts C–C glycosylation to successfully afford the core structure of marmycin A. This methodology has been successfully applied to the genuine anthraquinone moiety leading to the natural product and simpler structural analogues.
    Mots-clés : anthraquinone, Friedel–Crafts, Key words marmycin, MACO, natural products, POLE 1, total synthesis, Ullmann.

  • P. Hazel, S. H. B. Kroll, A. Bondke, M. Barbazanges, H. Patel, M. J. Fuchter, R. C. Coombes, S. Ali, A. G. M. Barrett, et P. S. Freemont, « Inhibitor Selectivity for Cyclin-Dependent Kinase 7: A Structural, Thermodynamic, and Modelling Study », ChemMedChem, vol. 12, nᵒ 5, p. 372-380, 2017.
    Résumé : Deregulation of the cell cycle by mechanisms that lead to elevated activities of cyclin-dependent kinases (CDK) is a feature of many human diseases, cancer in particular. We identified small-molecule inhibitors that selectively inhibit CDK7, the kinase that phosphorylates cell-cycle CDKs to promote their activities. To investigate the selectivity of these inhibitors we used a combination of structural, biophysical, and modelling approaches. We determined the crystal structures of the CDK7-selective compounds ICEC0942 and ICEC0943 bound to CDK2, and used these to build models of inhibitor binding to CDK7. Molecular dynamics (MD) simulations of inhibitors bound to CDK2 and CDK7 generated possible models of inhibitor binding. To experimentally validate these models, we gathered isothermal titration calorimetry (ITC) binding data for recombinant wild-type and binding site mutants of CDK7 and CDK2. We identified specific residues of CDK7, notably Asp155, that are involved in determining inhibitor selectivity. Our MD simulations also show that the flexibility of the G-rich and activation loops of CDK7 is likely an important determinant of inhibitor specificity similar to CDK2.
    Mots-clés : cancer, CDK7, drug discovery, isothermal titration calorimetry, MACO, POLE 1, protein kinases.

  • M. Malacria, N. Della Ca’, E. Motti, et G. Maestri, « Palladium- and Norbornene-Catalyzed Synthesis of Highly Functionalized Thiophenes: The Remarkable Effect of Electron-Poor Olefins as Ligand », HETEROCYCLES, vol. 95, nᵒ 2, p. 753, 2017.

  • A. Monfredini, V. Santacroce, L. Marchiò, R. Maggi, F. Bigi, G. Maestri, et M. Malacria, « Semi-Reduction of Internal Alkynes with Prototypical Subnanometric Metal Surfaces: Bridging Homogeneous and Heterogeneous Catalysis with Trinuclear All-Metal Aromatics », ACS Sustainable Chemistry & Engineering, vol. 5, nᵒ 9, p. 8205-8212, sept. 2017.
    Résumé : Suitably delocalized metal–metal bonds can stabilize a particular class of discrete trinuclear complexes that are the transition-metal counterparts of carbon-based aromatics. This chemical stability has pivoted the development of an advantageous catalytic method for the semireduction of internal alkynes under transfer hydrogenation condition. The reaction does not require any additional solvent and a simple workup delivers pure products. This combines with broad functional group tolerance, complete cis-selectivity and catalytic charges down to 100 ppm on multigram scale.
    Mots-clés : MACO, POLE 1.

  • V. Santacroce, R. Duboc, M. Malacria, G. Maestri, et G. Masson, « Visible-Light, Photoredox-Mediated Oxidative Tandem Nitroso-Diels–Alder Reaction of Arylhydroxylamines with Conjugated Dienes », European Journal of Organic Chemistry, vol. 2017, nᵒ 15, p. 2095-2098, 2017.
    Résumé : Arylhydroxylamines were used in the nitroso-Diels–Alder reaction to generate in situ nitrosoarenes under visible-light, catalytic and aerobic conditions. Mixing a solution of aryl- or heteroarylhydroxylamines with conjuguated dienes in the presence of a catalytic amount of Ru(bpy)3Cl2 afforded 3,6-dihydro-1,2-oxazines in good yields under an oxygen atmosphere.
    Mots-clés : MACO, Nitrogen heterocycles, Nitroso-Diels–Alder reaction, Oxidative tandem, Photocatalysis, POLE 1, Radicals.

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