Martel, Arnaud
Martel, Arnaud
FORMATION ET EXPERIENCES PROFESSIONNELLES
Depuis Sep 2013 : Professeur des Universités, IUT Le Mans
Sep 2004-Sep 2013 Maître de conférences, IUT du Mans.
Dec 2010 Habilitation à diriger les recherches, Chimie, Université du Maine, Le Mans.
Avril 2003-Septembre 2004 Université d’Uppsala (Suède), Chercheur post-doctorant dans l’équipe du Dr. Henrik Ottosson. Bourse Marie Curie.
Etude théorique assistée d’outils de modélisation moléculaire, puis synthèse de 2-silenolates chiraux.
Mars 2002-Mars 2003 ICOA (Institut de chimie organique et analytique) Université d’Orléans, Chercheur Post-doctorant. Financement industriel.
Recherche sur un projet industriel au sein de l’équipe du Pr. Guillaumet. Synthèse de méthylènemalonates.
Sep 2001 Doctorat Chimie Fine, Chimie Organique (mention très honorable), Université du Maine, Le Mans.
Titre : Hétérocycloaddition stéréocontrôlées d’éthers d’énols de cétones cycliques - Accès aux 9-décanolides.
1997 D.E.A Chimie Fine : Élaboration de biomolécules et matériaux organiques (Modules optionnels : Matériaux organiques, Théorie orbitalaire et mécanismes réactionnels ; mention bien), Université du Maine cohabilité avec l’Université de Nantes.
1996 Maîtrise de Chimie (Module optionnel : Physicochimie des polymères, mention assez-bien), Université du Maine, Le Mans.
1994 D.U.T Chimie , IUT Le Mans, Université du Maine.
ENSEIGNEMENTS
IUT Chimie Le Mans.
Disciplines enseignées : Chimie Analytique, Informatique, Modélisation Moléculaire, Organocatalyse.
RESPONSABILITES ET MANDATS
- Responsable de la licence professionnelle Analyse chimique et contrôle des matériaux
- élu au conseil d'administration de l'IUT du Mans
- élu au CFVU
- élu au conseil d'unité de l'IMMM
Projet Solarchéochimie
Collaboration : Aline Durand (Porteur), Arthur Laenger (Doctorant).
Le projet Solarchéochimie est construit sur une collaboration avec le Creeah (Laboratoire d'archéologie du Mans et porte sur l'analyse chimie de sédiments archéologiques.
Malgré les avancées des méthodes prospectives, les archéologues peinent à évaluer l’extension des sites, leur organisation et leur caractérisation avant et pendant la fouille. En l’absence de foyers, de mobilier discriminant, ils ont du mal à caractériser les aires d’activités d’une structure et de leurs annexes ou la fonction exacte d’un bâtiment, et, donc, à différencier spatialement et fonctionnellement certains des bâtis mis au jour. Pour y pallier, le projet mobilise l’analyse chimique multiélémentaire systématisée des sols archéologiques pour mieux les caractériser et pour construire un outil de prospection géochimique évaluatif du sous-sol. Un atlas de référence des profils de sols a été initié.
Etude mécanistique de réactions par DFT. Exemples : études de réactions d'allylboration
Collaboration avec l'institut des sciences chimiques de Rennes : François Carreaux, Joelle Vidal et Claudia Lalli.
Une collaboration autour de l'étude DFT de réactions d'allylboration catalysée par le Binol a été initiée pour mettre en évidence les mécanismes réactionnels mis en jeu.
Publications
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Laenger, A., Martel, A., Boucher, F., François, X., Dabas, M., Rouillard, J., & Durand, A. (2022). Comparison of geophysical prospecting and geochemical prospecting at the medieval and modern Cistercian Abbey of Carnoët (Finistère, France). Archaeological Prospection, 1– 10. https://doi.org/10.1002/arp.1875
- Zhang, X.; Ligny, R.; Chewchanwuttiwong, S.; Hadade, R.; Laurent, M. Y.; Martel, A.; Jacquemmoz, C.; Lhoste, J.; Bricaud, S.; Py, S.; Dujardin, G., δ-Valerolactamic Quaternary Amino Acid Derivatives: Enantiodivergent Synthesis and Evidence for Stereodifferentiated β-Turn-Inducing Properties. J. Org. Chem. 2021, 86, (12), 8041-8055.
- Gavelle, S.; Abid, I.; Biletskyi, B.; Henrion, S.; Hémon-Ribaud, A.; Lhoste, J.; Martel, A.; Dujardin, G.; Gaulon-Nourry, C., TIPS-Diazoacetone Aldol Addition: Mechanistic Aspects and Contribution to the Synthesis. J. Org. Chem. 2021, 86, (7), 4917-4931.
- Rouzier, F.; Sillé, R.; Montiège, O.; Tessier, A.; Pipelier, M.; Dujardin, G.; Martel, A.; Nourry, A.; Guillarme, S., Synthesis of Constrained C-Glycosyl Amino Acid Derivatives Involving 1,3-Dipolar Cycloaddition of Cyclic Nitrone as Key Step. European Journal of Organic Chemistry 2020, 2020, (43), 6749-6757.
- Martel, A.; Dhal, R.; Gaulon, C.; Laurent, M. Y.; Dujardin, G., Dihydropyrans by Cycloadditions of Oxadienes. In Organic Reactions, Wiley: 2020; Vol. 101, pp 1-550.
- El Bouakher, A.; Martel, A.; Comesse, S., α-Halogenoacetamides: versatile and efficient tools for the synthesis of complex aza-heterocycles. Organic & Biomolecular Chemistry 2019, 17, (37), 8467-8485.
- Nocquet, P.-A.; Macé, A.; Legros, F.; Lebreton, J.; Dujardin, G.; Collet, S.; Martel, A.; Carboni, B.; Carreaux, F., Stereodivergent approach in the protected glycal synthesis of L-vancosamine, L-saccharosamine, L-daunosamine and L-ristosamine involving a ring-closing metathesis step. Beilstein Journal of Organic Chemistry 2018, 14, 2949-2955.
- Mabit, T.; Siard, A.; Legros, F.; Guillarme, S.; Martel, A.; Lebreton, J.; Carreaux, F.; Dujardin, G.; Collet, S., Stereospecific C-Glycosylation by Mizoroki–Heck Reaction: A Powerful and Easy-to-Set-Up Synthetic Tool to Access α- and β-Aryl-C-Glycosides. Chemistry – A European Journal 2018, 24, (53), 14069-14074.
- Gallier, F.; Martel, A.; Dujardin, G., Enantioselective Access to Robinson Annulation Products and Michael Adducts as Precursors. Angew. Chem. Int. Ed. 2017, 56, (41), 12424-12458.
- El Bouakher, A.; Tasserie, J.; Le Goff, R.; Lhoste, J.; Martel, A.; Comesse, S., Chemo-, Regio-, and Stereoselective Synthesis of Polysusbtituted Oxazolo[3,2-d][1,4]oxazepin-5(3H)ones via a Domino oxa-Michael/aza-Michael/Williamson Cycloetherification Sequence. J. Org. Chem. 2017, 82, (11), 5798-5809.
- Enantioselective 1,3-DC reactions of C-Carboxy Ketonitrones and Enals with MacMillan catalyst: Evidence of a non-concerted mechanism (Arnaud Martel - Ben Ayed - K.; Laurent - M. Y.; Martel - A.; Selim - K. B.; Abid - S.; Dujardin - G., European Journal of Organic Chemistry, 2017, (45), 6763-6774)
Highly diastereo- and enantioselective 1,3-dipolar cycloadditions between functional ketonitrones and β-substituted enals are promoted by organocatalysis with the imidazolidinium catalyst of MacMillan. Study of the scope of the reaction shows that high selectivities are conserved by varying the N-protecting group or the ester function. However it is sensitive to sterical interaction with the C-substituent of the nitrone. Reaction proceeds in all cases with a high exo selectivity. In most cases, a third diastereomer, not compatible with a concerted mechanism, was observed, although in minute amount. DFT calculations evidence that the cycloaddition proceeds in a non-concerted fashion by a first oxa Michael-type addition of the nitrone to the double bond followed by a cyclization. This mechanism explains the formation of the observed minor diastereomers. In addition, the diastereo- and enantioselectivities of the reaction were shown to be intermediately thermodynamically controlled and the diastereomeric ratio is modulated by the kinetics of iminium hydrolysis.
- Oxa–diketopiperazines: Access and Conformational Analysis of Potential Turn Inducers (Arnaud Martel - Dr. Mathéo Berthet - Aurélien Lebrun - Prof. Arnaud Martel - Thomas Cheviet - Prof. Jean Martinez and Dr. Isabelle Parrot, ChemistrySelect 2017, 2 (21), 5824-5827.)
An improvement of the 1,2,5-oxadiazine-3,6-diones (Oxd) synthesis and reactivity is described in this paper. The methodology has been successfully applied to produce a library of this poorly studied scaffold, which can be considered as an oxa-diketopiperazine (oxa-DKP). Significantly, the first crystal structures of oxa-DKP were obtained and compared to the diketopiperazine ring. Finally, a straightforward procedure concerning the coupling of various amino acids with oxa-DKP heterocycles to afford original peptidomimetics was reported. The conformational analysis realized on di- and tripeptide analogs revealed that the oxa-DKP skeleton exhibited remarkable β-turn inducer properties.
- Synthesis of Oxazolidin-4-ones: Domino O-Alkylation/Aza-Michael/Intramolecular Retro-Claisen Condensation (Arnaud Martel - Abderrahman El Bouakher - Ronan Le Goff - Jordan Tasserie - Jérôme Lhoste - Arnaud Martel - and Sébastien Comesse, 2016)
An original and rapid domino reaction for access to oxazolidin-4-ones is presented. Simply by heating α-bromoamido alcohol in the presence of KNaCO3 and water with readily prepared Michael acceptors, an unprecedented molecular rearrangement is generated. This new methodology enables the hitherto unreported synthesis of functionalized oxazolidin-4-ones. The process was proved to be compatible with a wide variety of substrates, and high regioselectivities were achieved.
- Practical and Cost-Effective Method for the Synthesis of Bicyclo[2.2.2]octane-1,4-dicarboxylic Acid (Arnaud Martel - Le Marquer Nicolas - Laurent Mathieu Yves, 2015)
A short and efficient synthesis of bicyclo[2.2.2]octane-1,4-dicarboxylic acid involving the formation of a semicarbazone is developed, and a reproducible protocol for the redn. of this semicarbazone is described. The use of microwaves significantly shortens the duration of the sequence to the diacid compared to the previously described synthetic method. In addn., by shifting from the use of large amts. of Raney nickel to a solid-phase process, both the safety and cost are improved notably.
- [3+2] Route to quaternary oxaprolinol derivatives as masked precursors of disubstituted β3,β3-amino aldehyde (Arnaud Martel - Shpak-Kraievskyi Pavlo - Mankou Makaya Amelle - Beauchard Anne - Laurent Mathieu Y. - Dujardin Gilles, 2015)
Bicyclic isoxazolidines displaying one or two quaternary stereocenter(s) were formed starting from functional cyclic ketonitrones equipped with a Ph glycinol chiral auxiliary. The products were engaged in stereocontrolled 1,3-dipolar cycloaddn. reactions with a range of electron-rich and electron-poor dipolarophiles. A new reductive removal of the Ph glycinol chiral auxiliary was introduced and was shown to afford chemoselectively a quaternary isoxazolidine deriv. (of oxaprolinol-type) without cleaving the N-O isoxazolidine bond. Keeping the aldehyde function masked as a cyclic pseudo-acetal, the liberated oxy-amine function was shown to be available for a pseudo-peptide coupling with various N-protected amino acids. The isoxazolidine ring was opened by a reductive N-O bond cleavage, giving a pseudo-dipeptide that was C-terminated with an aldehyde function.
- Simple Access to Highly Functional Bicyclic gamma- and delta-Lactams: Origins of Chirality Transfer to Contiguous Tertiary/Quaternary Stereocenters Assessed by DFT. (Arnaud Martel - Le Goff Ronan - Sanselme Morgane - Lawson Ata Martin - Daich Adam - Comesse Sebastien, 2015)
This paper describes the synthesis of both polysubstituted oxazolo-pyrrolidinones and -piperidinones by a domino process. The methodol. is based on the reaction between hydroxyl halogenoamides and Michael acceptors, which leads efficiently to bicyclic lactams. The process is compatible with unsym. electron-withdrawing groups on the Michael acceptor, which allows the formation of two contiguous and fully controlled tertiary and quaternary stereocenters. In the case of tetrasubstituted Michael acceptors, two adjacent quaternary stereocenters are formed in good yield. Starting from (R)-phenylglycinol derived amides results in the formation of enantio-enriched bicyclic lactams in low to good yields and with high levels of stereoselectivity, thus greatly increasing the scope and interest of this strategy. The origins of chirality transfer and diastereoselectivity were studied by DFT calcns. and have been attributed to a kinetic control in one of the last two steps of the reaction sequence. This selectivity is dependent upon both the substituents on the Michael acceptor and the sodium cation chelation.
- Asymmetric access to α-substituted functional aspartic acid derivatives by a [3+2] strategy employing a chiral dienophile (Arnaud Martel - Ben Ayed Kawther - Beauchard Anne - Poisson Jean-Francois - Py Sandrine - Laurent Mathieu Y. - Ammar Houcine - Abid Souhir - Dujardin Gilles, 2014)
Enantiopure vinyl ethers of Stericol underwent diastereoselective thermal 1,3 dipolar cycloaddns. with N-benzyl, N-benzhydryl, and N-PMB aspartate ester nitrones. Chemoselective N-debenzylation of the resulting cycloadducts afforded diastereomerically and enantiomerically pure cryst. NH-isoxazolidine, the abs. configuration of which was established by X-ray crystallog. N-Protection and N-O cleavage of this isoxazolidine gave enantioenriched quaternary aspartate derivs. bearing functionalized side chains.
- Asymmetric Synthesis of α,α-Disubstituted Amino Acids by Cycloaddition of (E)-Ketonitrones with Vinyl Ethers (Arnaud Martel - Xiaofei Zhang - Pascale Cividino - Jean-François Poisson - Pavlo Shpak-Kraievskyi - Mathieu Y. Laurent - Gilles Dujardin - and Sandrine Py, 2014)
Original acyclic (E)-α,α-dialkylketonitrones bearing a chiral auxiliary on their nitrogen atom were synthesized and successfully employed for the asymmetric synthesis of α,α-disubstituted amino acids using regio- and stereocontrolled 1,3-dipolar cycloaddition reactions with vinyl ethers. N-Glycosyl chiral auxiliaries were found to provide excellent exo- and π-facial stereocontrol. The obtained enantiopure cycloadducts were selectively transformed into functional α,α-disubstituted amino acids and related β-peptides through the highly regioselective opening of an intermediate quaternary anhydride.
- Enantioselective Ruthenium-Catalyzed 1,3-Dipolar Cycloadditions between C-Carboalkoxy Ketonitrones and Methacrolein: Solvent Effect on Reaction Selectivity and Its Rational (Arnaud Martel - Khalid B. Selim - Mathieu Y. Laurent - Jérôme Lhoste - Sandrine Py - and Gilles Dujardin, 2014)
A catalytic 1,3-dipolar cycloaddition between carboalkoxy ketonitrones and methacrolein under the effect of chiral ruthenium Lewis acid (R,R-1) was developed with high regio-, diastereo-, and enantiocontrol. The diastereochemical outcome of the cycloaddition reaction is marked by a significant solvent effect, and a divergent endo or exo control can be tuned by an appropriate choice of both the solvent and the N- and O-substituents of the ketonitrone. A rationale of the solvent effect, based on the computational study of the interactions between the methacrolein–Ru complex and its counteranion (SbF6–), is proposed to explain the selectivities obtained.
- Organocatalytic enantio- and diastereoselective 1,3-dipolar cycloaddition between alanine-derived ketonitrones and E-crotonaldehyde: efficiency and full stereochemical studies (Arnaud Martel - Khalid B. Selim - Anne Beauchard - Jérôme Lhoste - Mathieu Y. Laurent - Gilles Dujardin, 2012)
Highly enantio- and exo-selective 1,3-dipolar cycloadditions of alanine-derived ketonitrones to E-crotonaldehyde could be realized in a good yield by the use of a chiral imidazolidinone salt without the addition of water. The origin of the stereoselectivity in the reaction was discussed and the absolute configuration of the cycloadduct determined unambiguously.
- Domino Process Optimized via ab Initio Study for an Alternative Access to Bicyclic Lactams (Arnaud Martel - Sébastien Comesse - Adam Daïch, 2011)
A totally new acid-free domino process to access highly functionalized bicyclic γ- and δ-lactams starting from commercially available and inexpensive ethoxymethylene derivatives is reported. Mechanisms elucidated by computational calculations led to new reaction conditions that boosted the yields up to 3.5 times higher.
- A Convergent Hetero-Diels-Alder Strategy for Asymmetric Access to a Lactone Containing Two Lipidic Chains (Arnaud Martel - Vu Cong S. - Guisot Nicolas - Guillarme Stephane - Dujardin Gilles - Pipelier Muriel - Dubreuil Didier - Saluzzo Christine, 2012)
Eu(fod)3-catalyzed hetero-cycloaddn. of chiral β-alkyl-N-vinyl-1,3-oxazolidin-2-ones with a hetero-diene bearing a lipidic chain led to hetero-cycloadducts in high yield with excellent endo and facial selectivities. An original lipidic lactone I, a potent precursor of a ceramide analog, was obtained in seven steps from the adduct in a convergent manner after appropriate functionalization.
