References of "Olive, Gilles"
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See detailFrench Mnemonics for the Periodic Table
Olive, Gilles ULg; Riffont, David

in Journal of Chemical Education (2008), 85(11), 1489-1490

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See detailSynthesis of New Tetraethyl(N-alkyl-1-aminoethan-1,1-diyl)bisphosphonates and ESR Analysis of Chemical Exchange of Derived Nitroxides of Acyclic Aminobisphosphonates.
Olive, Gilles ULg; Rockenbauer, Antal; Rozanska, Xavier et al

in Phosphorus, Sulfur & Silicon & the Related Elements (2007), 182(10), 2359-2369

The synthesis and the full characterization of two new linear bisphosphonates(tetraethyl(N-tert-butyl-1-aminoethan-1,1-diyl)bisphosphonate and tetraethyl(Nsec-butyl-1-aminoethan-1,1-diyl)bisphosphonate ... [more ▼]

The synthesis and the full characterization of two new linear bisphosphonates(tetraethyl(N-tert-butyl-1-aminoethan-1,1-diyl)bisphosphonate and tetraethyl(Nsec-butyl-1-aminoethan-1,1-diyl)bisphosphonate), and the first analysis of the ESR spectra of the corresponding nitroxides is reported. The preliminary results of theoretical calculations on model compounds suggest a small B0 (in the McConnell equation). The results of bisphosphonate ester and bisphosphonic acid are similar. The discrepancies of P coupling for the diphosphorus compound stems from B2 that is different when the dihedral angle is larger than 90◦. [less ▲]

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See detailESR Investigation of Chemical Exchange in Geminally Diphosphorylated Linear Nitroxide Radicals
Rockenbauer, Antal; Olive, Gilles ULg; Rozanska, Xavier et al

in Journal of Physical Chemistry A (2004), 108(25), 5484-5489

For geminally diphosphorylated linear nitroxide radicals, a marked line width alternation (LWA) can be observed. The LWA appears irrespectively whether the investigated radicals R¢¢N(O¥)C(P(O)(OEt)2)2R¢ ... [more ▼]

For geminally diphosphorylated linear nitroxide radicals, a marked line width alternation (LWA) can be observed. The LWA appears irrespectively whether the investigated radicals R¢¢N(O¥)C(P(O)(OEt)2)2R¢ contain any chiral group or not. If R¢¢ ) tert-butyl and R¢ ) H, the small â-hydrogen coupling indicates a completely blocked rotation around the N-C ó-bond and the LWA can be assigned to a chemical exchange between conformations in which the phosphoryl groups have a symmetric and a nonsymmetric geometry. The conformational change is accompanied by the deformation of the CP2 bonding angle and the rate of exchange is slowed in pentane for which the solvent molecules can be trapped by the chelating phosphoryl groups. If R¢¢ ) benzyl, both the proton hyperfine lines of the CH2 group and the phosphorus lines of the CP2 group produce a LWA; two coalescences can be observed. In the case of a chiral R¢¢ group (R¢¢ ) secondary butyl, R¢ ) methyl) a tentative four-site model can explain the highly complex LWA. [less ▲]

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See detailLarge phosphorus hyperfine coupling as a sensitive tool for studying molecular dynamics : ESR and Molecular Mechanics studies of ring interconversion in cis-2,5-diphosphoryl-2,5-dimethyl-pyrrolidinoxyl radical
Rockenbauer, Antal; Gaudel-Siri, Anouk; Siri, Didier et al

in Journal of Physical Chemistry A (2003), 107(19), 3851-3857

ESR spectra of cis- and trans-â-diphosphorylated pyrrolidine-N-oxyl radicals, c-1 and t-1, were studied in liquid and frozen solution. The expected 1:2:1 triplet (aP (2)) of the 1:1:1 triplet (aN) was ... [more ▼]

ESR spectra of cis- and trans-â-diphosphorylated pyrrolidine-N-oxyl radicals, c-1 and t-1, were studied in liquid and frozen solution. The expected 1:2:1 triplet (aP (2)) of the 1:1:1 triplet (aN) was observed for t-1; however, for c-1, the inner lines of the 1:2:1 triplet showed a dramatic broadening characteristic of chemical exchange between two equivalent conformations. Owing to the large difference in the hyperfine splitting constants (hfsc) of the exchanging phosphorus (¢aP 21 G), the coalescence temperature was unusually high (193 K, in n-pentane), and the potential barrier for ring interconversion (10.5 kJ mol-1) was easily obtained from the temperature dependence of the exchange rate. This value was in very good agreement with the value obtained for an empirical pseudorotational potential (11 kJ mol-1) that was adjusted to fit the temperature dependence of the phosphorus hfsc. For c-1, molecular mechanics calculations gave similar characteristics for the pseudorotational potential and indicated the existence of two identical minima with distorted geometries lying between 3T4 and 3E or 4T3 and E3. For t-1, only the 3T4 conformer was found to be significantly populated. Frozen solution spectra showed that the phosphorus hfsc anisotropy is higher when the C-P bond is pseudoaxial; this result can be explained by a geometry-dependent delocalization of the unpaired electron into the phosphorus 3p orbitals. [less ▲]

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See detailOptimization, continuation and lack of the one-step diphosphorylation reaction. Assay of modification of the tetraethyl(pyrrolidine-2,2-diyl)bisphosphonate
Olive, Gilles ULg; Jacques, Alain

in Phosphorus, Sulfur & Silicon & the Related Elements (2003), 178(1), 33-46

The optimization of the one-step diphosphorylation reaction is reported. The synthesis of new ®-aminobisphosphonates with four- and sixmembered rings and acyclic species with several substituents on the ... [more ▼]

The optimization of the one-step diphosphorylation reaction is reported. The synthesis of new ®-aminobisphosphonates with four- and sixmembered rings and acyclic species with several substituents on the nitrogen atom and on the carbon atom bearing the two phosphorus atoms is described. [less ▲]

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See detailControl of the Radical Polymerization by 2,2,15,15-tetramethyl-1-aza-4,7,10,13-tetraoxacyclopentadecan-1-oxyl and its Sodium Salt
Olive, Gilles ULg; Rozanska, Xavier; Smulders, Wilfred et al

in Macromolecular Chemistry and Physics (2002), 203(12), 1790-1796

The control of the radical polymerization of styrene by 2,2,15,15-tetramethyl-1-aza-4,7,10,13-tetraoxacyclopentadecan-1-oxyl is reported here in bulk at 90 °C, 120 °C and in miniemulsion. Similarly, the ... [more ▼]

The control of the radical polymerization of styrene by 2,2,15,15-tetramethyl-1-aza-4,7,10,13-tetraoxacyclopentadecan-1-oxyl is reported here in bulk at 90 °C, 120 °C and in miniemulsion. Similarly, the control by its sodium complex is reported in bulk at 90 °C. [less ▲]

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See detailA biomimetic synthesis of coelenterazine analogs
Devillers, Ingrid; Arrault, Axelle; Olive, Gilles ULg et al

in Tetrahedron Letters (2002), 43(17), 3161-3164

N-(Trifluoroacetyl)dehydrodipeptides 2–3 were coupled to aminomethylene dimethylacetal derivatives 4–5. The resulting pseudo-tripeptides 6 were stepwise deprotected (carbonyl function (7) then amine ... [more ▼]

N-(Trifluoroacetyl)dehydrodipeptides 2–3 were coupled to aminomethylene dimethylacetal derivatives 4–5. The resulting pseudo-tripeptides 6 were stepwise deprotected (carbonyl function (7) then amine function) and in situ cyclized into imidazolopyrazines 1. [less ▲]

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See detailSynthesis of 2-Diethoxyphosphoryl-2-Methyl-5-Phenyl-3,4-Dihydro-2H-Pyrrole-1-Oxide (DEPMPO-Ph): a New Radical Spin-Trap
Olive, Gilles ULg; Le Moigne, François; Mercier, Anne et al

in Symposium Drug Discovery Strategies: from Leads to Drugs (2001, November 16)

The synthesis of a new radical spin trap is presented here: the 2-Diethoxyphosphoryl-2-Methyl-5-Phenyl-3,4-Dihydro-2H-Pyrrole-1-Oxide (DEPMPO-Ph)

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See detailTetraethyl(Pyrrolidine-2,2-diyl)Bisphosphonate
Olive, Gilles ULg; Jacques, Alain

in Molecules (2001), 6

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See detailA 1H, 13C, 31P and 15N NMR study of (pyrrolidine-2,2-diyl)bisphosphonic acid, tetraalkyl(pyrrolidine-2,2-diyl)bisphosphonates and acyclic tetraethyl bisphosphonates
Olive, Gilles ULg; van Genderen, Marcel H P

in Magnetic Resonance in Chemistry [=MRC] (2000), 38(5), 379-381

A multinuclear magnetic resonance study (1H, 13C, 31P, 15N) was performed on a series of new cyclic pyrrolidine bisphosphonates and acyclic bisphosphonates. Values are reported and discussed for the ... [more ▼]

A multinuclear magnetic resonance study (1H, 13C, 31P, 15N) was performed on a series of new cyclic pyrrolidine bisphosphonates and acyclic bisphosphonates. Values are reported and discussed for the chemical shifts and coupling constants of the various nuclei. [less ▲]

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See detailZwitterionic (pyrrolidine-2,2-diyl)bisphosphonic acid at 100, 150 and 293K
Olive, Gilles ULg; Ellis, Dianne D; Siri, Didier et al

in Acta Crystallographica Section C-Crystal Structure Communications (2000), C56(6), 720-722

Structure of the zwitterionic pyrrolidine-2,2-diylbis(phosphonic acid) at 100, 150 and 293 K

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See detail2-ethoxycarbonyl-2-methyl-3,4-dihydro-2H-pyrrole-1-oxide: evaluation of the spin trapping properties
Olive, Gilles ULg; Mercier, Anne; Le Moigne, François et al

in Free Radical Biology & Medicine (2000), 28(3), 403-408

The 2-ethoxycarbonyl-2-methyl-3,4-dihydro-2H-pyrrole-l-oxide (EMPO), an easily prepared pyrroline-Noxide has been tested as a free radical scavenger. Spin adducts of superoxide, hydroxyl radical, and ... [more ▼]

The 2-ethoxycarbonyl-2-methyl-3,4-dihydro-2H-pyrrole-l-oxide (EMPO), an easily prepared pyrroline-Noxide has been tested as a free radical scavenger. Spin adducts of superoxide, hydroxyl radical, and other free radicals were characterized in phosphate buffer at pH 7.0 and 5.6. At pH 7 in phosphate buffer, the EMPO/O2 2• spin adduct was estimated to be about five times more persistent than its DMPO analogue. Furthermore, its decay does not produce the EMPO/HO• adduct. [less ▲]

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See detailOne-Step Gem-Diphosphorylation of Amides and Lactams
Olive, Gilles ULg; Le Moigne, François; Mercier, Anne et al

in Synthetic Communications (2000), 30(4), 619-627

We report the extension of an easy one-step synthesis of amino gem-bisphosphonates through the reaction of amides and lactams with trialkykphosphites

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See detailThe Nitroxides in Polymerization
Olive, Gilles ULg; Göttgens, Christianne; Smulders, Wilfred et al

Poster (1999, May 20)

The Nitroxides in Polymerization arepresented here with explanation.

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See detailAlkoxyamine-mediated Controlled Radical Polymerization in Emulsion
Smulders, Wilfred; Göttgens, Christianne; Olive, Gilles ULg et al

Poster (1998, November)

Alkoxyamine-mediated Controlled Radical Polymerization in Emulsion is presented here.

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See detailSynthèse de Nouvelles Nitrones du Type Pyrroline-N-Oxyde et leur Utilisation en Spin-Trapping
Olive, Gilles ULg

Doctoral thesis (1998)

In the field of the design of new free radical scavengers, especially for the ESR study of the role played by oxygen-centered species, such as superoxide and hydroxyl radical, involved in biological ... [more ▼]

In the field of the design of new free radical scavengers, especially for the ESR study of the role played by oxygen-centered species, such as superoxide and hydroxyl radical, involved in biological processes, the laboratory recently reported the synthesis of a new nitrone, the 2- diethoxyphosphoryl-2-methyl-3,4-dihydro-2H-pyrrole-1-oxide (DEPMPO). This nitrone was shown to be more efficient than the widely used 2,2-dimethyl-3,4-dihydro-2H-pyrrole-1-oxide (DMPO) : the superoxide spin adduct DEPMPO-OOH has a significantly larger half-life than DMPO-OOH, it does not decompose spontaneously into DEPMPO-OH, and DEPMPO is less sensitive to nucleophilic addition of water than DMPO. Such a behavior is related to the introduction of a -P(O)(OEt)2 group in the 2-position of the ring. In the present work, we tried to investigate the electronic and steric effects of the phosphorus moiety. Then, we prepared 3 new nitrones, the 2-diethoxyphosphorylmethyl-2-methyl-3,4-dihydro-2H-pyrrole-1-oxide (ESP), the 2,2-bisdiethoxyphosphoryl-3,4-dihydro-2H-pyrrole-1-oxide (DPBO) and the 2- ethoxycarbonyl-2-methyl-3,4-dihydro-2H-pyrrole-1-oxide (EMPO). In ESP, the introduction of a methylene between the ring and the -P(O)(OEt)2 group leads to a decrease of the electrowithdrawing effect, and the behaviour of this nitrone toward the spin trapping of superoxide is more similar to that of DMPO. For DPBO, the second phosphorylated group does not seem to stabilize the DPBO-OOH adduct. In the case of EMPO, the -P(O)(OEt)2- group is replaced by -CO2Et, which has a lower electrowithdrawing effect. The overall behavior of this nitrone is much closer to that of DEPMPO. The most important difference in the spin trap properties of all these nitrones is the persistance of their superoxide spin adduct. Other nitrones are currently investigated in the laboratory. [less ▲]

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See detailSynthesis of Tetraalkyl(Pyrrolidine-2,2-diyl)bisphosphonates and 2,2-Bis(diethoxyphosphoryl)-3,4-dihydro-2H-pyrrole 1-Oxide; ESR Study of Derived Nitroxides
Olive, Gilles ULg; Le Moigne, François; Mercier, Anne et al

in Journal of Organic Chemistry (1998), 63(24), 9095-9099

Synthesis of Tetraalkyl (Pyrrolidine-2,2-diyl)bisphosphonates and 2,2-Bis(diethoxyphosphoryl)-3,4-dihydro-2Hpyrrole 1-Oxide; ESR Study of Derived Nitroxides

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See detail5-(Diethoxyphosphorylmethyl)-5-methyl-4,5-dihydro-3H-pyrrole N-oxide : Synthesis and Evaluation of Spin Trapping Properties
Roubaud, Valérie; Mercier, Anne; Olive, Gilles ULg et al

in Journal of the Chemical Society. Perkin Transactions 2 (1997), 9

A new spin trap, the 5-(diethoxyphosphorylmethyl)-5-methyl-4,5-dihydro-3H-pyrrole N-oxide (3), is prepared through a four-step synthetic route. The in vitro spin trapping properties of 3 have been ... [more ▼]

A new spin trap, the 5-(diethoxyphosphorylmethyl)-5-methyl-4,5-dihydro-3H-pyrrole N-oxide (3), is prepared through a four-step synthetic route. The in vitro spin trapping properties of 3 have been investigated and the hydroxyl and superoxide spin adducts characterised. The persistence of the superoxide spin adduct obtained with 3 is compared with those of the analogues obtained with DEPMPO [5-(diethoxyphosphoryl)-5-methyl-4,5-dihydro-3H-pyrrole N-oxide] and DMPO in both phosphate buffer and pyridine. In 0.1 M phosphate buffer at pH 7.0, the HOO-3? adduct is found to be 2.8 times more persistent than HOO-DMPO?, but 5.7 times less than HOO-DEPMPO?. In phosphate buffer, HOO-3? decomposes to give HO-3?. The stereoselectivity of the addition of free radicals on 3 is generally poor, and mixtures of diastereomers have been observed by EPR. The overall spin trapping behaviour of nitrone 3 is more similar to that of DMPO than that of DEPMPO. [less ▲]

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See detailCombined Ring Inversion and Side Group Rotation in Geminal Diphosphoryl Substituted Pyrrolinoxyl Radicals: ESR Analysis of Chemical Exchange between Four Nonequivalent Sites
Rockenbauer, Antal; Mercier, Anne; Le Moigne, François et al

in Journal of Physical Chemistry A (1997), 101(43), 7965-7970

The ESR spectra of three diphosphorylated pyrrolidinoxyl radicals have been studied over a large temperature range. While for the trans 2,5-disubstituted compound 1 no line width alternation was found ... [more ▼]

The ESR spectra of three diphosphorylated pyrrolidinoxyl radicals have been studied over a large temperature range. While for the trans 2,5-disubstituted compound 1 no line width alternation was found, for the 2,2-disubstituted compounds 2 and 3, dramatic changes in the spectra were observed as a function of the temperature. These changes were explained by a four-site chemical exchange model including both ring inversion and hindered rotation around the carbon-phosphorus bonds. For radical 3, the presence of additional 5,5-dimethyl substitution can completely block rotations around carbon-phosphorus bonds for certain ring geometries, while for other ring conformations chemical exchange still occurs through combined inversionrotation processes. An effective two-site model composed of nonequivalent sites and a superposition model composed of a pair of exchanging conformers and a pair of nonexchanging conformers were used to simulate spectrum variations. A satisfactory fit was obtained over the entire temperature range investigated. From the temperature dependence of the exchange frequencies the potential barriers for ring inversion (27 kJ/mol), for combined inversion-rotation (11 kJ/mol), and for rotation around the carbon-phosphorus bonds (14 kJ/mol) were estimated. [less ▲]

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See detail31P Labeled cyclic nitrones : a new class of spin traps for free radicals in biological milieu
Barbati, Stéphane; Clément, Jean Louis; Olive, Gilles ULg et al

in Minisci, Francesco (Ed.) Free Radicals in Biology and Environment (1997)

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