Network


Latest external collaboration on country level. Dive into details by clicking on the dots.

Hotspot


Dive into the research topics where Jean-Marc Sotiropoulos is active.

Publication


Featured researches published by Jean-Marc Sotiropoulos.


Journal of the American Chemical Society | 2012

Imidazol(in)ium Hydrogen Carbonates as a Genuine Source of N-Heterocyclic Carbenes (NHCs): Applications to the Facile Preparation of NHC Metal Complexes and to NHC-Organocatalyzed Molecular and Macromolecular Syntheses

Mareva Fevre; Julien Pinaud; Alexandre Leteneur; Yves Gnanou; Joan Vignolle; Daniel Taton; Jean-Marc Sotiropoulos

Anion metathesis of imidazol(in)ium chlorides with KHCO(3) afforded an easy one step access to air stable imidazol(in)ium hydrogen carbonates, denoted as [NHC(H)][HCO(3)]. In solution, these compounds were found to be in equilibrium with their corresponding imidazol(in)ium carboxylates, referred to as N-heterocyclic carbene (NHC)-CO(2) adducts. The [NHC(H)][HCO(3)] salts were next shown to behave as masked NHCs, allowing for the NHC moiety to be readily transferred to both organic and organometallic substrates, without the need for dry and oxygen-free conditions. In addition, such [NHC(H)][HCO(3)] precursors were successfully investigated as precatalysts in two selected organocatalyzed reactions of molecular chemistry and polymer synthesis, namely, the benzoin condensation reaction and the ring-opening polymerization of d,l-lactide, respectively. The generation of NHCs from [NHC(H)][HCO(3)] precursors occurred via the formal loss of H(2)CO(3)via a concerted low energy pathway, as substantiated by Density Functional Theory (DFT) calculations.


Chemistry: A European Journal | 2010

Room-Temperature, Ligand- and Base-Free Heck Reactions of Aryl Diazonium Salts at Low Palladium Loading: Sustainable Preparation of Substituted Stilbene Derivatives

François-Xavier Felpin; Jean-Marc Sotiropoulos; Eric Fouquet; Oier Ibarguren; Julia Laudien

The Pd(OAc)(2)-catalyzed Heck reaction of aryl diazonium salts with 2-arylacrylates led to cis-stilbenes with good to excellent stereoselectivity. The environmentally friendly protocol developed in this work features low palladium loading in technical-grade methanol at room temperature under base-, additive-, and ligand-free conditions. The same protocol applied to simple Heck coupling of aryl diazonium salts with methyl acrylate allows astonishingly low palladium loading, down to 0.005 mol%. The stereoselectivity experimentally observed for the synthesis of cis-stilbenes has been rationalized by DFT calculations. Moreover, the role of methanol in promoting the reaction has been clarified by a computational study.


Angewandte Chemie | 2008

Highly Diastereoselective Synthesis of Orthoquinone Monoketals through λ3-Iodane-Mediated Oxidative Dearomatization of Phenols†

Laurent Pouységu; Stefan Chassaing; Delphine Dejugnac; Anne-Marie Lamidey; Jean-Marc Sotiropoulos; Stéphane Quideau

Orthoquinone monoketals A and orthoquinols B are cyclohexa-2,4-dienone derivatives with valuable reactivity features for the construction of complex molecular architectures. Their conjugated dienone unit and the vicinal positioning of their oxygenated functionalities constitute a unique structural arrangement that can be transformed rapidly into various kinds of polyoxygenated (poly)cyclic systems (Scheme 1).


Journal of Organic Chemistry | 2012

Imidazolium Hydrogen Carbonates versus Imidazolium Carboxylates as Organic Precatalysts for N-Heterocyclic Carbene Catalyzed Reactions

Mareva Fevre; Paul Coupillaud; Jean-Marc Sotiropoulos; Joan Vignolle; Daniel Taton

Imidazolium-2-carboxylates (NHC-CO(2) adducts, 3) and (benz)imidazolium hydrogen carbonates ([NHC(H)][HCO(3)], 4) were independently employed as organic precatalysts for various molecular N-heterocyclic carbene (NHC) catalyzed reactions. NHC-CO(2) adducts were obtained by carboxylation in THF of related free NHCs (2), while the synthesis of [NHC(H)][HCO(3)] precursors was directly achieved by anion metathesis of imidazolium halides (1) using potassium hydrogen carbonate (KHCO(3)) in methanolic solution, without the need for the prior preparation of free carbenes. Thermogravimetric analysis (TGA) and TGA coupled with mass spectrometry (TGA-MS) of most [NHC(H)][HCO(3)] precursors 4 showed a degradation profile in stages, with either a concomitant or a stepwise release of H(2)O and CO(2), between 108 and 280 °C, depending on the nature of the azolium and substituents. In solution, NHC generation from both [NHC(H)][HCO(3)] salts and NHC-CO(2) adducts could be achieved at room temperature, most likely by a simple solvation effect. Both types of precursors proved efficient for organocatalyzed molecular reactions, including cyanosilylation, benzoin condensation, and transesterification reactions. The catalytic efficiencies of NHC-CO(2) adducts 3 were found to be approximately 3 times higher than those of their [NHC(H)][HCO(3)] counterparts 4.


Angewandte Chemie | 2012

Synthesis and Characterization of an Isolable Base‐Stabilized Silacycloprop‐1‐ylidene

Ricardo Rodriguez; Thibault Troadec; Tsuyoshi Kato; Nathalie Saffon-Merceron; Jean-Marc Sotiropoulos; Antoine Baceiredo

Strained but stable: An isolable silacycloprop-1-ylidene stabilized by intramolecular complexation with an iminophosphorus ylide fragment was successfully synthesized and fully characterized. The formation of this small highly strained cyclic silylene involves an unprecedented Si(IV)→Si(II) rearrangement under very mild conditions.


Chemistry: A European Journal | 2012

Sustainable Heck–Matsuda Reaction with Catalytic Amounts of Diazonium Salts: An Experimental and Theoretical Study

Nicolas Susperregui; Jean-Marc Sotiropoulos; François Le Callonnec; Eric Fouquet; François-Xavier Felpin

The palladium-catalyzed Heck-Matsuda reaction with a catalytic amount of an in-situ-generated diazonium salt proceeded under mild and sustainable conditions. The reaction proceeded at room temperature, under base-free conditions, and only generated tBuOH, H(2)O, and N(2) as by-products. Ortho-substituted diazonium salts were more-efficiently coupled to methyl acrylate than their corresponding para isomers, which required the addition of anisole as an additive. In support of these experimental data, we carried out theoretical studies to gain a deeper understanding of these reaction outcomes.


Inorganic Chemistry | 2012

Bis(amidinato)germylenerhodium complexes: synthesis, structure, and density functional theory calculations.

Dimitri Matioszek; Nathalie Saffon; Jean-Marc Sotiropoulos; Annie Castel; Jean Escudié

The first monogermylenerhodium complexes stabilized by bulky amidinato ligands on the divalent germanium center have been synthesized and characterized by NMR spectroscopy and X-ray crystallography. Their stability strongly depends on the steric hindrance of the amidinato ligand. With trimethysilyl groups on the nitrogen atoms of the amidinato ligand, only the germylene oxide rhodium complex could be obtained; by contrast, with t-Bu groups, the germylenerhodium complex was isolated. In both cases, the formation of amidinatorhodium complexes was observed. The donating ability of the germylene ligand has been assessed from the CO stretching frequency of the corresponding dicarbonylrhodium complex and was confirmed by density functional theory calculations.


Chemistry: A European Journal | 2014

Cyclodimerization versus Polymerization of Methyl Methacrylate Induced by N-Heterocyclic Carbenes: A Combined Experimental and Theoretical Study

Winnie Nzahou Ottou; Damien Bourichon; Joan Vignolle; Anne-Laure Wirotius; Frédéric Robert; Yannick Landais; Jean-Marc Sotiropoulos; Daniel Taton

The activation behavior of two N-heterocyclic carbenes (NHCs), namely, 1,3-bis(isopropyl)imidazol-2-ylidene(NHCiPr) and 1,3-bis(tert-butyl) imidazol-2-ylidene (NHCtBu), as organic nucleophiles in the reaction with methyl methacrylate (MMA) is described. NHCtBu allows the polymerization of MMA in DMF at room temperature and in toluene at 50 °C, whereas NHCiPr reacts with two molecules of MMA, forming an unprecedented imidazolium-enolate cyclodimer (NHCiPr/MMA=1:2). It is proposed that the reaction mechanism occurs by initial 1,4-nucleophilic addition of NHCiPr to MMA, generating a zwitterionic enolate 2, followed by addition of 2 to a second MMA molecule, forming a linear imidazolium-enolate 3 (NHCiPr/MMA=1:2). Proton transfer, generating intermediate 5, followed by cyclization and release of methanol yielded the aforementioned zwitterionic cyclodimer 1:2 adduct 7, the molecular structure of which has been established by NMR spectroscopy, X-ray diffraction, and mass spectrometry. This unexpected difference between NHCtBu and NHCiPr in the reaction with MMA (polymerization and cyclodimerization, respectively) can be rationalized by using DFT calculations. In particular, the nature of the NHC strongly influences the cyclodimerization pathway, the cyclization of 5 and the release of methanol are the discriminating step and limiting step, respectively. In the case of NHCtBu, both steps are strongly disfavoured compared with that of NHCiPr (energetic difference of around 14 and 9 kcal mol(-1), respectively), preventing the cyclization mechanism from a kinetic viewpoint. Moreover, addition of a third molecule of MMA in the polymerization pathway results in a lower activation barrier than that of the limiting step in the cyclodimerization pathway (difference of around 14 kcal mol(-1)), in agreement with the formation of polymethyl methacrylate (PMMA) by using NHCtBu as nucleophile.


Chemical Science | 2013

Unexpected rearrangements in the synthesis of an unsymmetrical tridentate dianionic N-heterocyclic carbene

Emmanuelle Despagnet-Ayoub; Jean-Marc Sotiropoulos; Lawrence M. Henling; Michael W. Day; Jay A. Labinger; John E. Bercaw

Starting from the same ethylenediamine species, three valuable carbene precursors were synthesized under differing conditions: a tridentate dianionic N-heterocyclic carbene bearing an aniline, a phenol and a central dihydroimidazolium salt, its benzimidazolium isomer by intramolecular rearrangement and a dicationic benzimidazolium-benzoxazolium salt by changing the Bronsted acid from HCl to HBF_4. A DFT study was performed to understand the rearrangement pathway. The structure of a bis[(NCO)carbene] zirconium complex was determined.


Organic Letters | 2016

Total Synthesis of (−)-Bacchopetiolone via an Asymmetric Hydroxylative Phenol Dearomatization/[4+2]-Dimerization Cascade Promoted by a Novel Salen-Type Chiral Iodane

Romain Coffinier; Mourad El Assal; Philippe A. Peixoto; Cyril Bosset; Jean-Marc Sotiropoulos; Laurent Pouységu; Stéphane Quideau

The first total and biomimetic synthesis of the natural bis(sesquiterpene) (-)-bacchopetiolone (revised structure) was completed through a highly diastereoselective hydroxylative phenol dearomatization/[4+2]-dimerization cascade conversion of (+)-curcuphenol using a novel C2-symmetrical chiral Salen-type bis(λ(5)-iodane).

Collaboration


Dive into the Jean-Marc Sotiropoulos's collaboration.

Top Co-Authors

Avatar

G. Pfister-Guillouzo

Centre national de la recherche scientifique

View shared research outputs
Top Co-Authors

Avatar
Top Co-Authors

Avatar
Top Co-Authors

Avatar
Top Co-Authors

Avatar

S. Labat

Centre national de la recherche scientifique

View shared research outputs
Top Co-Authors

Avatar

Alain Igau

Centre national de la recherche scientifique

View shared research outputs
Top Co-Authors

Avatar

Anna Chrostowska

Centre national de la recherche scientifique

View shared research outputs
Top Co-Authors

Avatar
Top Co-Authors

Avatar
Top Co-Authors

Avatar
Researchain Logo
Decentralizing Knowledge