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POLI Giovanni
Professor

Université Pierre et Marie Curie Paris 6,
4 Place Jussieu, 75252 Paris cedex 5

Couloir 32-42 4ème étage
Team ROCS

Office 414
Tel:33(0)1 44 27 41 14

mail:



Research interests:

  • Organic chemistry, Organometallic catalysis, Organic synthesis, Domino processes, Heterocycles.

Current research:

In general:

  • Studies on new transfromations via step- and atom-economical organometallic catalysis towards organic synthesis.
  • Comprehension and optimization of selectivity (enantio- and diastereoselectivity).
  • Conception of successive catalytic transformations allowing the formation of highly complex molecules in a single chemical step.
  • Synthesis of heterocyclic molecules with a potential biological interest.

_In particular:

  • Development of allylic C-H activation reactions, nucleopalladation, allylation, cross-coupling reactions, carbonylations,…
  • Catalyzed domino processes (pure, type I and type II).
  • Synthesis of molecules from the podophyllotoxin family.
  • Organometallic catalysis in aerobic and isohypsic conditions.

Recent Results:

Enantioselective Synthesis of Aryl Sulfoxides via Palladium-Catalyzed Arylation of Sulfenate Anions Org. Lett. 2007, 9, 5493-5496

This paper shows the power of sulfenate anion chemistry in palladium catalysis, that was discovered in 2005 in our lab. Such anions are generated and engaged in situ in palladium-catalyzed coupling reactions with allyl acetates or aryl halides. This paper shows the formation of enantioenriched sulfoxides with induction predictability. This method is one of the few methods for the asymmetric synthesis of sulfoxides.

Allylic Alkylation and Ring-Closing Metathesis in Sequence: a Successful Cohabitation of Pd and Ru Org. Lett. 2008, 10, 405-408

We proposed a taxonomy for catalytic domino sequences: pure (single catalytic cycle), pseudo-domino (two or more catalytic cycles). These can in turn be classified into type I (one catalyst) and type II (two or more catalysts). This study shows the first result of our team in a pseudo-domino type II double allylic alkylation / metathesis sequence.

Striking AcOH Acceleration in Direct Intramolecular Allylic Amination Reaction Chem. - Eur. J. 2009, 15, 11078-11082

This paper can be considered as our first investigation in the field of C-H activation. Our study shows that direct allylic amination can be accelerated through addition of acetic acid. Detailed DFT calculations gave us insightful information about the mechanistic, structural and energetic aspects in the palladium reoxidation step.

New Cross-Coupling Based Synthesis of Carpanone Org. Lett. 2009, 11, 4378-4381

This work shows our contribution to the total synthesis of carpanone, a natural product interesting the chemists community since the 70’s. We succeeded in synthesizing this natural product in six chemical steps with 55% overall yield from sesamol. This synthesis, which is up-to-date the most efficient reported, involves a Suzuki-Miyaura cross-coupling reaction for the direct introduction of the prenyl chain. A Pd(II)-catalyzed biomimetic coupling generated then carpanone in a fully diastereoselctive manner.

γ- and δ-Lactams via Pd-Catalyzed Intramolecular Allylic Alkylation: Enantioselective Synthesis, NMR Investigations, and DFT Rationalization Synlett 2009, 1441-1444; Chem. Eur. J., 2011, 17, 2885-2896

In 1998, we published a new approach for the synthesis of 3,4-disubstituted γ-lactames via an palladium-catalyzed intramolecular alkylation. These studies show the development of an asymmetric version for this transformation. The second very detailed paper enjoyed the collaboration of Profs. Per-Ola Norrby (Göteborg) and Peter Fristrup (Copenhagen) for calculations and Prof. Paul Pregosin (Zürich) for the spectroscopy part.

Pd-Catalyzed Domino Carbonylative / Decarboxylative Allylation: An Easy and Selective Monoallylation of Ketones
Chem. Commun., 2012, 48, 5889-5891; Adv. Synth. Catal. doi: 10.1002/adsc.201200378

We developed a synthetic procedure for the selective formation of γ,δ-aromatic ketones from easily prepared α-chloroacetophenones. The method, which is based on a palladium-catalyzed carbonylative allylation/decarboxylation pseudo-domino process, is completely insensitive to the electronic properties of the substituents on the aromatic ring.

Scientific background:

  • 1979 – 1980: Laurea internship (MSc.), Università degli Studi di Milano (Supervisor: Prof. Carlo Scolastico)
  • 1980 – 1985: Ph. D. at Università degli Studi di Milano (Supervisor: Prof. Carlo Scolastico)
  • 1983: Diploma from Politecnico di Milano (Milan, Italy, Organic chemistry)
  • 1985 – 1987: First postdoctoral position at Université de Genève (Geneva, Switzerland) under the supervision of Prof. Wolfgang Oppolzer.
  • 1987 – 1988: Second postdoctoral position at Université de Genève (Teaching assistant) under the supervision of Prof. Wolgang Oppolzer.
  • 1988 - 1989 Teaching assistant at Université de Lausanne (Lausanne, Switzerland, independant research)
  • 1990 - 1992: Associate researcher at Università degli Studi di Milano (Milan, Italy).
  • 1992 – 2000: Professor (2ème classe) at Università degli Studi di Firenze (Florence, Italy).
  • 1999 – 2000: Associate professor at Université Pierre et Marie Curie (Paris, France).
  • 2000 – 2011: Professor (1ère classe) at Université Pierre et Marie Curie (Paris, France).
  • Since 2012: Professor (Classe Exceptionnelle) at Université Pierre et Marie Curie (Paris, France).

Selected papers:

  1. Maitro, G.; Vogel, S.; Sadaoui, M.; Prestat, G.; Madec, D.; Poli, G.
    Enantioselective Synthesis of Aryl Sulfoxides via Palladium-Catalyzed Arylation of Sulfenate Anions
    DOI: 10.1021/ol702343g
    Org. Lett. 2007, 9, 5493-5496
  2. Kammerer, C.; Prestat, G.; Gaillard, T.; Madec, D.; Poli, G.
    Allylic Alkylation and Ring-Closing Metathesis in Sequence: a Successful Cohabitation of Pd and Ru.
    DOI: 10.1021/ol702694v
    Org. Lett. 2008, 10, 405-408
  3. Nahra,F.; Liron, F.; Prestat, G.; Mealli, C.; Messaoudi, A.; Poli, G.
    Striking AcOH Acceleration in Direct Intramolecular Allylic Amination Reactions
    DOI: 10.1002/chem.200990164
    Chem. Eur. J., 2009, 15, 11078-11082
  4. Liron, F.; Fontana, F.; Zirimwabagabo, J-O.; Prestat, G.; Rajabi, J.; La Rosa, C.; Poli, G.
    A New Cross-Coupling Based Synthesis of Carpanone
    DOI: 10.1021/ol9017326
    Org. Lett. 2009, 11, 4378-4381
  5. Bantreil, X.; Prestat, G.; Moreno, A.; Madec, D.; Fristrup, P.; Norrby, P.O.; Pregosin, P. S.; Poli, G.
    γ- and δ-Lactams through Palladium-Catalyzed Intramolecular Allylic Alkylation: Enantioselective Synthesis, NMR Investigations, and DFT Rationalization
    DOI: 10.1002/chem.201001300
    Chem. Eur. J., 2011, 17, 2885-2896
  6. Giboulot, S.; Liron, F.; Prestat, G.; Wahl, B.; Sauthier, M.; Castanet, Y.; Mortreu, A.; Poli, G.
    Pd-Catalyzed Domino Carbonylative / Decarboxylative Allylation: An Easy and Selective Monoallylation of Ketones
    DOI: 10.1039/C2CC32391E
    Chem. Commun., 2012, 48, 5889-5891