Marion BARBAZANGES

Maîtresse de conférences

Sorbonne University
4 Place Jussieu, 75252 Paris cedex 5
Tower 32-42, 4th floor, office 416
CASCH Group
Phone : 33(0)1 44 27 39 32

Research interests

Organometallic Chemistry, Polymer Chemistry, Asymmetric Synthesis and Catalysis, Multi-steps Synthesis.

Scientific career

  • 2020: “Habilitation à Diriger des Recherches”
  • Since 09/2011: Maître de Conférences at Sorbonne Université UMR8232 (Paris, France)
  • 2010-2011 : Post-doctoral position at Université Pierre et Marie Curie (Paris VI, France) under the supervision of Dr C. Aubert: Organometallic chemistry.
  • 2009 : Post-doctoral position at Imperial College (London, UK) under the supervision of Pr. A.G.M. Barrett: Medicinal chemistry.
  • 2008 : Doctor from Pierre and Marie Curie University (Paris VI). Thesis carried out under the supervision of Professor J. Cossy – total synthesis of natural product and development of new synthesis methods.
  • 2005 : Master II Research in Organic et Bioorganic Chemistry at Université Pierre et Marie Curie (Paris VI, France).
  • 2005 : Ingénieur of Ecole Supérieure de Physiques et Chimie Industrielles (ESPCI, Paris, France).

Current research

  • Helicenes: Asymmetric Organometallic Synthesis and Catalysis

We have developed the synthesis and splitting of 8 [6]-helicene-chiral alcohols, aromatic or not, the key step of the synthesis of which is based on a cycloaddition of [2+2+2] catalyzed with cobalt. These alcohols made it possible to obtain helical chiral mono- and bisphosphinite ligands which turned out to be monodent and were used in metallocatalyzed cycloisomerization reactions of enynes.

We have highlighted a remarkable effect of the ligand/metal ratio in the palladocatalyzed Tsuji-Trost allylation reaction, when bisphosphinite-[6]helicenes are used as chirality inducers. We showed that by varying the quantity of ligand, the (R) and (S) isomeric products could be selectively obtained. The use of 31P NMR, XRD and DFT calculations made it possible to rationalize this result.

  • Cobalt chemistry

In collaboration with Marc Petit, we looked at the hydroelementation processes of C=N double bonds in the presence of low-valence cobalt catalysts. This work was the subject of C. Bories’ thesis (2019-23). The kinetic study, DFT calculations, NMR studies, deuteration experiments and X-ray diffraction analyzes allowed us to propose a catalytic cycle.

  • Chemistry of gold

We studied the well-known addition of propargyl acetates to olefins via an O-acyl migration/cyclopropanation sequence. We showed that the stereochemistry of the olefin strongly depends on the gold catalyst and the reaction parameters.

  • Chiral Anion Strategy in Asymmetric Organometallic Catalysis

Controlling the absolute configuration of new asymmetric centers is a major challenge in contemporary organometallic chemistry. It is traditionally enabled through the introduction of chiral ligands, or the use of enantioenriched substrates. In the “chiral counterion strategy,” the chiral information is carried by the counterion of the cationic metal species.

We have broadened the field of application of the chiral counterion strategy to the creation of carbon-carbon bonds, and more particularly to cycloisomerization and [2+2+2] cycloaddition reactions, to the use of cationic iridium and cationic rhodium as a metal as well as axial chirality.

  • Cycloisomerization reactions of 1,6-enynes catalyzed with Iridium(I)
  • Rhodium(I)-catalyzed [2+2+2] cycloaddition reactions

In order to optimize the induction of enantioselectivity, we looked at double stereodifferentiation, by introducing chiral information on both the ligand and the counterion of the cationic metal species.

  • Chiral Phosphate: Counterion or Ligand?

Using NMR (collaboration with E. Caytan), mass spectrometry (collaboration with D. Lesage) and DFT calculations (collaboration with V. Gandon), we studied the organometallic species involved in this transformation. Thus, we showed that, according to stoichiometry, the catalytic mixture [Rh(COD)Cl]2/dppb/Ag(S)-TRIP leads to two active species, in which the TRIP anion alternately has a counterion character. or type X ligand

Selected publications

  1. High-resolution cryo-EM of the human CDK-activating kinase for structure-based drug design.
    Cushing, V. I.; Koh, A. F.; Feng, J.; Jurgaityte, K.; Bondke, A.; Kroll, S. H. B.; Barbazanges, M.; Scheiper, B.; Bahl, A. K.; Barrett, A. G. M.; Ali, S.; Kotecha, A.; Greber, B. J. Nat. Commun202415, 2265. 
  2. Cobalt-Catalyzed bis-Borylation of Quinolines: The Importance of the Cobalt Triplet State
    Bories, C. C.; Gontard, G.; Barbazanges, M.; Lemière, G.; Petit, M. Chem. Eur. J2023, 29, e202303178. 
  3. Gold-catalyzed addition of propargyl acetates to olefins via O-acyl migration / cyclopropanation sequence: insight into the diastereoselective formation of the alkene
    Barbazanges, M.; Gimbert, Y.; Fensterbank, L. J. Org. Chem. 202388, 3297.
  4. Hydrido-Cobalt Complexes for the Chemo- and Regioselective 1,2-Silylative Dearomatization of N-Heteroarenes
    Bories, C. C.; Gontard, G.; Barbazanges, M.; Derat, E.; Petit, M. Org. Lett. 202325, 843.
  5. Implication of a Silyl Cobalt Dihydride Complex as a Useful Catalyst for the Hydrosilylation of Imines
    Bories, C. C.; Barbazanges, M.; Derat, E.; Petit, M. ACS Catal. 202111, 14262.
  6. Helical bisphosphinites in asymmetric Tsuji-Trost allylation : a remarkable P/Pd ratio effect
    Medena, C.; Aubert, C.; Derat, E.; Fensterbank, L.; Gontard, G.; Khaled, O.; Vanthuyne, N.; Ollivier, C.; Petit, M.; Barbazanges, M. ChemCatChem 202113, 4543-4548 avec Front cover
  7. HELIXOL-derived Bisphosphinite Ligand : Synthesis and Application in Gold-catalyzed Enynes Cycloisomerization
    Medena, C.; Calogero, F.; Lemoine, Q.; Aubert, C.; Derat, E.; Fensterbank, L.; Gontard, G.; Khaled, O.; Vanthuyne, N.; Moussa, J.; Ollivier, C.; Petit, M.; Barbazanges, M. Eur. J. Org. Chem. 2019, 2129.
  8. Chiral Phosphate in Rhodium-Catalyzed Asymmetric [2+2+2] Cycloaddition : Ligand, Counterion or Both ?
    Barbazanges, M.; Caytan, E.; Lesage, D.; Aubert, C.; Fensterbank, L.; Gandon, V.; Ollivier, C. Chem. Eur. J. 201622, 8553. Hot paper.
  9. Double Stereodifferentiation in Rhodium-Catalyzed [2+2+2] Cycloaddition : Chiral Ligand/Chiral Counterion Matched Pair
    Augé, M.; Feraldi-Xypolia, A.; Barbazanges, M.; Aubert, C.; Fensterbank, L.; Gandon, V.; Kolodziej, E.; Ollivier, C. Org. Lett. 201517, 3754.
  10. 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 201447, 6652.

Other activities

Participation in the European Erasmus+ LABVIRT project, for teaching practical work remotely