Marie-Joëlle Eymin

University of Burgundy, Dijon, Bourgogne, France

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Publications (6)15.29 Total impact

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    ABSTRACT: The synthesis of o-boronato- and o-trifluoroborato-phosphonium salts supported by the L-amino acid side chain is described. The synthesis of this new class of amino acid derivatives was achieved by stereoselective quaternization of o-(pinacolato)boronatophenylphosphine with beta- or gamma-iodo amino acid derivatives which are prepared from L-serine or L-aspartic acid, respectively. The quaternization of the phosphine was performed using either iodo amino ester or carboxylic acid derivatives. In addition, free carboxylic acid and amine derivatives were obtained by saponification or HCl acidolysis of o-boronato-phosphonium amino esters, respectively. The usefulness of these compounds in peptide coupling was demonstrated by coupling an o-boronato-phosphonium amino ester with an aspartic acid moiety. When the o-boronato-phosphonium amino acid or dipeptide derivatives were mixed with fluoride, the corresponding o-trifluoroborated products were cleanly and rapidly obtained in high isolated yields. The hydrolysis of these compounds at room temperature using a phosphate buffer pH 7/CD3CN mixture shows only traces of free fluoride F- after several days. Finally, a preliminary radiolabelling assay has demonstrated the facile [18F]-fluoride incorporation and high stability of the radiolabelled product in aqueous conditions. Indeed, this new class of boron-phosphonium amino acid derivatives shows promising properties for applications in synthesis and labelling of peptides.
    No preview · Article · Apr 2015 · The Journal of Organic Chemistry
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    ABSTRACT: The synthesis of phosphonium-boronate amino acid derivatives was achieved by quaternization of o-boronatophenylphosphine with iodo-amino acid derivatives. Preliminary radiolabelling studies demonstrate the facile 18F-fluoride trapping and the high stability of the trifluoroborato products in aqueous conditions, making these new compounds very promising for molecular imaging of peptides and proteins using PET.
    No preview · Article · May 2014 · Phosphorus Sulfur and Silicon and the Related Elements
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    Mathieu Dutartre · Jérôme Bayardon · Marie-Joëlle Eymin · Sylvain Jugé
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    ABSTRACT: A new stereoselective synthesis of P-chirogenic secondary phosphine oxides was described, by hydrolysis of aminophosphine borane prepared from ephedrine, then decomplexation. These compounds were used for the preparation of P-chirogenic diphosphine dioxides and biarylphosphine oxides, thanks to the aryne chemistry.
    Preview · Article · May 2014 · Phosphorus Sulfur and Silicon and the Related Elements
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    ABSTRACT: The stereoselective synthesis of a new classes of boronato- or trifluoroborato aminoacids and peptides was described using Wittig and C-H iridium borylation as key reactions. A trifluoroborato-thiophene aminoacid derivative showed an excellent stability in aqueous conditions, useful for further applications as radiotracers by 18F labeling.
    No preview · Article · May 2014 · Phosphorus Sulfur and Silicon and the Related Elements
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    ABSTRACT: The first P-chirogenic mono- and diphosphine ligands supported on the upper rim of a calix[4]arene moiety were synthesized using the ephedrine methodology. The lithiated calix[4]arene mono- and dianions both react with the oxazaphospholidine?borane, prepared from ephedrine, to afford regio- and stereoselectively the corresponding calix[4]arenyl aminophosphine?boranes, by cleavage of the heterocyclic ring at the P?O bond position. Subsequent reactions with HCl and then organolithium reagent and finally decomplexation with DABCO lead to the corresponding calix[4]arenyl mono- or diphosphines. Both enantiomers of the calix[4]arenyl phosphines were obtained either by using (+)- or (?)-ephedrine or by changing the addition order of the organolithium reagents during the synthesis. The enantiomeric excesses of the phosphines were determined either by HPLC on a chiral column of their borane complexes or by 31P NMR in the presence of a chiral palladium complex. The absolute configurations of the mono- and diphosphinocalix[4]arenes were assigned by X-ray analysis of their crystalline borane complexes. The P-chirogenic calix[4]arenyl phosphines were tested for asymmetric palladium-catalyzed allylic substitution of (E)-1,3-diphenylprop-2-en-1-yl acetate, by dimethyl malonate or benzylamine. When the bis-methylphenylphosphino calix[4]arene was used, the allylic products were obtained with 82% and 79% ee, respectively. In both cases, the use of a diphosphine affords better results than using 2 equivalents of monophosphine. Despite the C2 symmetry of the P-chirogenic diphosphine calix[4]arene ligand, computer modeling of the corresponding Pd(allyl) complex shows a clear dissymmetry of the LUMO, which is in good agreement with a complexed ?1-allyl moiety and with the regio- and enantioselectivity of the Pd-catalyzed allylations.
    No preview · Article · May 2013 · Organometallics
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    ABSTRACT: An unprecedented series of titanocene-gold bi- and trimetallic complexes of the general formula [[(η(5)-C(5)H(5))(μ-η(5):κ(1)-C(5)H(4)(CH(2))(n)PPh(2))TiCl(2)](m)AuCl(x)](q+) (n = 0, 2, or 4; m = 1, x = 1, q = 0 or m = 2, x = 0, q = 1) have been prepared and characterized spectroscopically. The luminescence spectroscopy and photophysics of one of the compounds, [[(η(5)-C(5)H(5))(μ-η(5):κ(1)-C(5)H(4)PPh(2))TiCl(2)](2)Au]PF(6), have been investigated in 2MeTHF solution and in the solid state at 77 and 298 K. Evidence for interfragment interactions based on the comparison of electronic band positions and emission lifetimes, namely, triplet energy transfer (ET) from the Au- to the Ti-containing chromophores, is provided. The cytotoxicity of the complexes was evaluated on A2780 ovarian cancer cells and on their cisplatin-resistant cell line A2780cisR; the compounds showed activity in the low micromolar range that was markedly more active than the corresponding titanocene-phosphine precursors [(η(5)-C(5)H(5))(η(5)-C(5)H(4)(CH(2))(n)PPh(2))TiCl(2)], cisplatin, and, for some of them, the gold analogue [(PPh(3))AuCl]. In an attempt to draw preliminary structure-activity relationships, cell uptake measurements and interaction studies with plasmid DNA and the model protein ubiquitin (Ub) have been undertaken on some of the compounds.
    No preview · Article · Aug 2011 · Inorganic Chemistry