Institut Parisien de Chimie Moléculaire

Research interests


Organic Chemistry

Current research

• Organometallic electrophilic catalysis (Au, Pt, Ir, Ag)
• Single Electron organometallic catalysis (Fe, Cu)
• Radical chemistry
• Photochemistry, photocatalysis, photoredox catalysis
• Mechanistic studies (DFT)
• Heterochemistry (silicon chemistry, NHC-boranes, new phosphine ligands)
• Total synthesis
• Mechanistic determinations
• Molecules with properties (natural products, probes, ligands)
• Synthetic biology
• Functionalized gold nanoparticles

Scientific career

• 2019 : Invited Professor at Okayama University
• Since 2017 : Director of IPCM
• 2017 : Invited Professor at Okayama Prefecture University
• 2017 : Silver Medal of the CNRS
• 2016 : Fellow of the Royal Society of Chemistry ; Prize of the Organic Division of the French Chemical Society
• 2014 : Clavel Lespiau Prize of the Académie des Sciences
• 2009 : Visiting Scientist Australian National University
• 2008-13 : Junior Member of IUF
• 2007-14 : Director of Master de Chimie de Paris Centre
• 2004 : Professor at UPMC
• 2001 : Habilitation à Diriger des Recherches
• 1995-2004 : CNRS researcher
• 1994-95 : Temporary lecturer position (Laboratory of Max Malacria)
• 1993 : Ph. D. State University of New York at Stony Brook (Advisor : Scott Sieburth)
• 1990 : Engineering degree from Ecole Supérieure de Chimie Industrielle de Lyon

Selected recent results

1/ Cycloisomerizations of polyunsaturated systems catalyzed by electrophilic complexes (Au, Pt, Ag…). New ligands.

• Application to the total synthesis of natural products (neomerane skeletons)
  
  
  Org. Chem. Front. 2017, 4, 1906, doi : 10.1039/c7qo00360a Link

  
  
  
  
  
  
  

• Polymerization by polycyclopropanation
  
  
  Macromolecules 2014, 47, 19, 6652, DOI : 10.1021/ma501516s Link

  
  
  

2/ New radical processes

Our group has a strong interest in photoredox catalysis and we have developed several pathways for the activation of C-X bonds for the formation of alkyl or aryl radicals.

• Activation of C-O and C-N bonds of epoxides or aziridines

• C-O reductive cleavage : photocatalytic Barton-McCombie deoxygenation

• C-S cleavage on sulfoniums for the formation of aryl radicals

• C-I cleavage on iodoniums for the formation of aryl radicals

• Cascades processes via trifluoromethylation

• Silicates as radical precursors
  In 2015, we have devised the first photocatalytic oxidation bis-catecholato silicates to provide unstabilized primary radicals. These radicals can be engaged in radical reactions (allylations, conjugate additions) and in nickel-catalyzed cross-coupling reactions (dual catalysis).

Various electrophiles can be used in the Ni-catalyzed cross coupling with alkyl radicals, for instance acylchorides. Reactions can be improved by flow synthesis.

In collaboration with Profs. Ryu and Fukuyama, multicomponent reactions involving a carbonylation step have been devised. 3 components to make ketones, 4 components to make amides !

• Use of non innocent ligands (NILs) in organometallic catalysis (C-H insertion and radical trifluoromethylation)

3/ Merging of gold catalysis with photoredox catalysis or photosensitization (energy transfer).

Upon blue LED irradiation, we have evidenced a dichotomic evolution of a reaction involving a vinylgold intermediate that depends on the electrophillc partner and the reaction conditions. With an aryldiazononium partner, a photoredox cycle is taking place generating an aryl radical which adds to gold (I) and which connects with the gold catalysis cycle to yield benzofurans.

In contrast, with an alkynyliodide, the first example of photosensitization of the vinylgold intermediate has been demonstrated.

4/ Heterochemistry
Sulfur chemistry, radical reactions (homolytic substitutions), bis-sulfoxide derivatives as reagents and ligands)

Silicon chemistry : new Lewis acids
We study the interactions of Martin’s spirosilane with different nucleophiles, from anionic ones to bulky Lewis bases.

An access to new NHC derivatives has been open.

Selected publications

1. A Parisian Vision of the Chemistry of Hypercoordinated Silicon Derivatives, Lemière, G. ; Millanvois, A. ; Ollivier, C. ; Fensterbank, L. Chem. Rec. 2021, 21, 1119 – 1129. Link
2. Visible-Light-Mediated Z-Stereoselective Monoalkylation of β,β-Dichlorostyrenes by Photoredox/Nickel Dual Catalysis, Abdellaoui, M. ; Millanvois, A. ; Levernier, E. ; Ollivier, C. ; Fensterbank, L. Synlett 2021, DOI : 10.1055/a-1374-9384.
3. Phenyl Silicates with Substituted Catecholate Ligands : Synthesis, Structural Studies and Reactivity Fensterbank, L. G. ; Levernier, E. ; Jaouadi, K. ; Zhang, H.-R. ; Corcé, V. ; Bernard, A. ; Gontard, G. ; Troufflard, C. ; Grimaud, L. ; Derat, E. ; Ollivier, C. Chem. Eur. J. 2021 DOI : 10.1002/chem.202100453
4. Amination of Cyclohexane by Dielectric Barrier Discharge Processing in a Continuous Flow Microreactor : Experimental and Simulation Studies, Lepoetre, A., Ognier, S., Zhang, M. ; Wengler, J. ; Al Ayoubi, S. ; Ollivier, C. ; Fensterbank, L. ; Duten, X. ; Tatoulian, M. Plasma Chem Plasma Process 2021 41, 351–368. Link
5. Lévêque, C. ; Levernier, E. ; Corcé, C. ; Fensterbank, L. ; Malacria, M. ; Ollivier ; C, Photoredox Catalysis, an Opportunity for Sustainable Radical Chemistry in Advanced Green Chemistry Part 2 : From Catalysis to Chemistry Frontiers, Horváth, I. T. and Malacria, M. Eds, World Scientific edition, pp. 49-121 (2020).
6. β-Cyclodextrin–NHC–Gold(I) Complex (β-ICyD)AuCl : A Chiral Nanoreactor for Enantioselective and Substrate-Selective Alkoxycyclization Reactions Tugny, C. ; del Rio, N. ; Koohgard, M. ; Vanthuyne, N. ; Lesage, D. ; Bijouard, K. ; Zhang, P. ; Meijide Suarez, J. ; Roland, S. ; Derat, E. ; Bistri-Aslanoff, O. ; Sollogoub, M. ; Fensterbank, L. ; Mouriès-Mansuy, V. ACS Catalysis 2020, 10, 5964-5972 Link
7. Direct Synthesis of N-Heterocyclic Carbene-Stabilized Copper Nanoparticles from an N-Heterocyclic Carbene Borane Frogneux, X. ; Hippolyte, L. ; Mercier, D. ; Portehault, D. ; Chanéac, C. ; Sanchez, C. ; Marcus, P. ; Ribot, F. ; Fensterbank, L. ; Carenco, S. Chem. Eur. J. 2019, 25, 11481-11485 Link
8. Photosensitized oxidative addition to gold(I) enables alkylynative cyclization of o-alkynylphenols with iodoalkynes Xia, Z. ; Corcé, V. ; Zhao, F. ; Przybylski, C. ; Espagne, A. ; Jullien, L. ; Le Saux, T. ; Gimbert, Y. ; Dossmann, H. ; Mouriès-Mansuy, V. ; Ollivier, C. ; Fensterbank, L. Nat. Chem. 2019, 11, 797-805. Link
9. Trifluoromethyl Radical Triggered Radical Cyclization of N-Benzoyl Ynamides Leading to Isoindolines M. Cassé, C. Nisole, H. Dossmann, Y. Gimbert, J.-M. Fourquez, L. Haberkorn, C. Ollivier and L. Fensterbank, Science China Chemistry 2019, 62, 1542-1546 Link
10. Carbonylation of Alkyl Radicals Derived from Organosilicates through Visible-Light Photoredox Catalysis Cartier, A. ; Levernier, E. ; Corcé, V. ; Fukuyama, T. ; Dhimane, A.-L. ; Ollivier, C. ; Ryu, I. ; Fensterbank, L. Angew. Chem. Int. Ed. 2019, 58, 1789-1793 Link
11. Artificial chiral metallo-pockets including a single metal serving as both structural probe and catalytic center Zhang, P. ; Tugny, C. ; Meijide Suárez, J. ; Guitet, M. ; Derat, E. ; Vanthuyne, N. ; Zhang, Y. ; Bistri, O. ; Mouriès-Mansuy, V. ; Ménand, M. ; Roland, S. ; L Fensterbank, L. ; Sollogoub, M. Chem. 2017, 3, 174-191 Link
12. Photoredox Catalysis for the Generation of Carbon Centered Radicals, Goddard, J.-P. ; Ollivier, O. ; Fensterbank, L., Acc. Chem. Res. 2016, 49, 1924-1936.Link
13. C–N bond Formation from a Masked High-Valent Copper Complex Stabilized by Redox Non-Innocent Ligands, Jacquet, J. ; Pauline Chaumont, Gontard, G. ; Orio, M. ; Vezin, H. ; Blanchard, S. ; Desage-El Murr, M. ; Fensterbank, L. Angew. Chem. Int. Ed. 2016, 55, 10712-10716.Link
14. Silicates as Latent Alkyl Radical Precursors : Visible-Light Photocatalytic Oxidation of Hypervalent Bis-Catecholato Silicon Compounds, Corcé, V. ; Chamoreau, L. M. ; Derat, E. ; Goddard, J.-P. ; Ollivier, C. ; Fensterbank, L., Angew. Chem. Int. Ed. 2015, 54, 11414-11418.Link
15. Molecular Complexity from Polyunsaturated Substrates. The Gold Catalysis Approach, Fensterbank, L. ; Malacria, M., Acc. Chem. Res. 2014, 47, 953-965. Link
16. Gold Catalyzed Polymerization Based on Carbene Polycyclopropanation, Nzulu, F. ; Bontemps, A., Robert, J. ; Barbazanges, M. ; Fensterbank, L. ; Goddard, J.-P. ; Malacria, M. ; Ollivier, C. ; Petit, M. ; Rieger, J. ; Stoffelbach, F. Macromolecules 2014, 47, 6652-6656. Link
17. Synthesis of Triangular Tripalladium Cations as Noble-Metal Analogues of the Cyclopropenyl Cation Blanchard, S. ; Fensterbank, L. ; Gontard, G. ; Lacôte, E. ; Maestri, G. ; Malacria, M. Angew. Chem. Int. Ed. 2014, 53, 1987-1991 Link
18. Atroposelective [2+2+2] Cycloadditions Catalyzed by a Rhodium(I)/Chiral Phosphate System Augé, M. ; Barbazanges, M. ; Tran, A. T. ; Simonneau, A. ; Elley, P. Amouri, H. ; Aubert, C. ; Fensterbank, L. ; Gandon, V. ; Malacria, M. ; Moussa, J. ; Ollivier, C. Chem. Commun. 2013, 7833-7835 Link
19. Iron-Catalyzed Reductive Radical Cyclization of Organic Halides in the Presence of NaBH4 : Evidence of an Active Hydrido Iron(I) Catalyst, Ekomié, A. ; Lefèvre, G. ; Fensterbank, L. ; Lacôte, E. ; Malacria, L. ; Ollivier, C. ; Jutand, A. Angew. Chem. Int. Ed. 2012, 51, 6942-6946.Link
20. Tracking Gold Acetylides in Gold(I)-Catalyzed Cycloisomerization Reactions of Enynes, Simonneau, A. ; Jaroschik, F. ; Lesage, D. ; Karanik, M. ; Guillot, R. ; Malacria, M. ; Tabet, J.-C. ; Goddard, J.-P. ; Fensterbank, L. ; Gandon, V. ; Gimbert, Y. Chem. Sci. 2011, 2 2417-2422.Link
21. Visible Light-Induced Photoreductive Generation of Radicals from Epoxides and Aziridines, Larraufie, M.-H. ; Pellet, P. ; Fensterbank, L. ; Goddard, J.-P. ; Lacôte, E. ; Malacria, M. ; Ollivier, C., Angewandte Chem. Int. Ed. 2011, 50, 4463-4466.Link
22. Oxidation of Trifluoroborates : An Opportunity for Tin-Free Radical Chemistry, Sorin, G. ; Martinez Mallorquin, R. ; Contie, Y. ; Baralle, A. ; Malacria, M. ; Goddard, J.-P. ; Fensterbank, L., Angewandte Chem. Int. Ed. 2010, 49, 8721-8723.Link
23. Radical Migration of Substituents of Aryl Groups on Quinazolinones Derived from N-Acyl Cyanamides, Larraufie, M.-H. ; Courillon, C. ; Ollivier, C. ; Lacote, E. ; Malacria, M. ; Fensterbank, L., J. Am. Chem. Soc. 2010, 132, 4381-4387. Link
24. Radical Synthesis of Guanidines from N-Acyl Cyanamides Larraufie, M.-H. ; Ollivier, C. ; Fensterbank, L. ; Malacria, M. ; Lacôte, E. Angew. Chem. Int. Ed. 2010, 49, 2178-2181 Link
25. Generation and Trapping of Cyclopentylidene Gold Species : Four Pathways to Polycyclic Compounds, G. Lemière, V. Gandon, K. Cariou, A. Hours, T. Fukuyama, A.-L. Dhimane, L. Fensterbank, M. Malacria, J. Am. Chem. Soc. 2009, 131, 2993-3006 Link