Synthesis of new substituted lactones by "click" chemistryRiva, Raphaël ; ; Jérôme, Robert et alin Arkivoc (2007), (x), 292-306 Several new oxepan-2-ones substituted by an ester, an ammonium, a hydroxyl, an acrylate and a poly(ethylene oxide) chain, respectively, were synthesized by the Huisgen's [3+2] cycloaddition of duly ... [more ▼] Several new oxepan-2-ones substituted by an ester, an ammonium, a hydroxyl, an acrylate and a poly(ethylene oxide) chain, respectively, were synthesized by the Huisgen's [3+2] cycloaddition of duly substituted alkynes onto 5-azidooxepan-2-one. [less ▲] Detailed reference viewed: 123 (23 ULg) Synthesis of new substituted poly(ε-caprolactone)s by comination of ring-opening polymerization, atom transfer radical addition and click reactionLecomte, Philippe ; Riva, Raphaël ; Schmeits, Stephanie et alPoster (2005, May 19) During the last few years, a great research effort has been devoted to the synthesis of aliphatic polyesters, e.g. poly(ε-caprolactone) and polylactides. Indeed, their remarkable properties of ... [more ▼] During the last few years, a great research effort has been devoted to the synthesis of aliphatic polyesters, e.g. poly(ε-caprolactone) and polylactides. Indeed, their remarkable properties of biodegradability and biocompatibility pave the way to many new applications in the biomedical field and as substitutes for non degradable polymers. In order to tailor the polyester properties, the grafting of functional groups along the polymer backbone is highly desirable. For the last few years, CERM has reported on the synthesis and the (co)polymerization of novel ε-caprolactones γ-substituted by various functional groups, e.g., ketal, ketone, olefin, protected alcohol and carboxylic acid. Nevertheless, the grafting of a specific functional group onto the aliphatic polyester backbone requires the synthesis of the parent substituted ε-caprolactone. There is accordingly a need for a strategy that would use a unique substituted ε-caprolactone, followed by derivatization by well-established reactions, so making available a wide range of pendent functional groups, polymeric or not. The derivatization reactions have however to be quantitative under mild conditions to prevent the aliphatic polyester from degrading. Moreover, these reactions must be compatible with the functional groups of interest, e.g., hydroxyl and carboxylic acid, in order to avoid the use of cumbersome protection/deprotection reactions. This communication aims at reporting that a-chloro-e caprolactone (αCLεCL) can be easily copolymerized with εCL into poly(αCLεCL-co-εCL) copolymers, which are precursors for various aliphatic polyesters, by using either Atom Transfer Radical Addition (ATRA) or Click reactions. The number of steps is limited whatever the "Click" or the "ATRA" strategy under consideration. In both cases, mild conditions have been found, such that degradation is minimized. Pendent hydroxyl, carboxylic acid and epoxide groups have been attached without using any protection/deprotection reaction. This strategy has been implemented for the synthesis of amphiphilic poly(εCL-g-ethylene oxide) graft copolymers, that have been used to prepare poly(D,L-lactide) nanoparticles for drug delivery applications. [less ▲] Detailed reference viewed: 49 (12 ULg) Synthesis of new substituted poly(ε-caprolactone)s by comination of ring-opening polymerization, atom transfer radical addition and click reactionRiva, Raphaël ; Schmeits, Stephanie ; Jérôme, Christine et alPoster (2005, June 01) Detailed reference viewed: 17 (5 ULg) Synthesis of new substituted polycaprolactones by ring-opening polymerizationJérôme, Robert ; Detrembleur, Christophe ; Lecomte, Philippe ![]() Conference (2000, May 02) Detailed reference viewed: 13 (2 ULg) Synthesis 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 ; ; et alin 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 ▲] Detailed reference viewed: 11 (0 ULg) The synthesis of no-carrier-added DL-4-[18F]fluorodeprenyl via the nucleophilic aromatic substitution reaction.Plenevaux, Alain ; ; et alin International Journal of Radiation Applications and Instrumentation. Part A : Applied Radiation and Isotopes (1991), 42(2), 121-7 No-carrier-added DL-alpha-methyl-beta-4-[18F]fluorophenyl-N-methyl-N-propynylethylamin e (DL-4-[18F]fluorodeprenyl) was synthesized via the following 3-step procedure: (1) nucleophilic aromatic ... [more ▼] No-carrier-added DL-alpha-methyl-beta-4-[18F]fluorophenyl-N-methyl-N-propynylethylamin e (DL-4-[18F]fluorodeprenyl) was synthesized via the following 3-step procedure: (1) nucleophilic aromatic substitution by [18F]fluoride on 4-nitrobenzaldehyde to produce 4-[18F]fluorobenzaldehyde (yield 65%); (2) the reaction of 4-[18F]fluorobenzaldehyde with (1-chloro-1-(trimethylsilyl)ethyl)lithium followed by hydrolysis to give 4-[18F]fluorophenylacetone (yield 50%); and (3) reductive alkylation of 4-[18F]fluorophenylacetone with N-methyl-propynylamine in the presence of NaBH3CN (yield 35%) followed by HPLC purification to give a racemic mixture of 4-[18F]fluorodeprenyl. The overall yield was 11% (EOB corrected), the synthesis time was 90 min and the specific activity greater than 0.57 Ci/mumol (end of synthesis). This synthesis approach, the conversion of an aromatic aldehyde to a homologous methyl ketone, extends the flexibility of the nucleophilic aromatic substitution reaction by applying it to the synthesis of radiotracers which do not bear electron-withdrawing activating groups on the aromatic ring. The tissue distribution of DL-4-[18F]fluorodeprenyl in mice at 1, 10 and 60 min was also measured and showed that metabolic defluorination was not significant. Clearance of radioactivity from brain after injection of DL-4-[18F]fluorodeprenyl was more rapid than that previously observed for [11C]L-deprenyl. [less ▲] Detailed reference viewed: 22 (3 ULg) SYNTHESIS OF NONACTIVATED F-18 FLUORINATED AROMATIC-COMPOUNDS THROUGH NUCLEOPHILIC-SUBSTITUTION AND DECARBOXYLATION REACTIONSPlenevaux, Alain ; Lemaire, Christian ; et alin Applied Radiation & Isotopes (1992), 43(8), 1035-1040 The synthesis of no-carrier-added 3-[F-18]fluoroanisole, 2-[F-18]fluoroanisole, [F-18]fluorobenzene and 4-[F-18]fluoroveratrole are reported. The strategy consists of amino-polyether supported ... [more ▼] The synthesis of no-carrier-added 3-[F-18]fluoroanisole, 2-[F-18]fluoroanisole, [F-18]fluorobenzene and 4-[F-18]fluoroveratrole are reported. The strategy consists of amino-polyether supported nucleophilic substitution with [F-18]F- on activated nitro aromatic aldehyde precursors followed by decarbonylation using Tris(triphenylphosphine) rhodium (I) chloride. The experimental parameters for this reaction have been studied and optimized with 2-[F-18]fluoro-4-methoxybenzaldehyde and then successfully applied to four other F-18-fluorinated aromatic aldehydes. The decarbonylation yields obtained were 84 +/- 5% (corrected for decay) within 15 min at 150-degrees-C in 1,4-dioxan. [less ▲] Detailed reference viewed: 25 (3 ULg) Synthesis of novel amphiphilic and pH-sensitive ABC miktoarm star copolymers; ; Jérôme, Robert et alPoster (2006, May 18) Detailed reference viewed: 12 (2 ULg) Synthesis of novel amphiphilic and pH-sensitive ABC miktoarm star terpolymersVan Butsele, Kathy ; ; Jérôme, Robert et alin Macromolecules (2006), 39(17), 5652-5656 Novel amphiphilic ABC miktoarm star terpolymers were synthesized that consist of hydrophilic poly( ethylene oxide) (PEO), hydrophobic poly(is an element of-caprolactone) (PCL), and pH-sensitive poly(2 ... [more ▼] Novel amphiphilic ABC miktoarm star terpolymers were synthesized that consist of hydrophilic poly( ethylene oxide) (PEO), hydrophobic poly(is an element of-caprolactone) (PCL), and pH-sensitive poly(2-vinylpyridine) (P2VP), thus a water-soluble block upon protonation. In the first step, poly( ethylene oxide monomethyl ether) (MPEO) was capped by one omega-epoxy end group by reaction of the original hydroxy end group with epichlorohydrin. MPEO-b-P2VP diblock copolymers were prepared by nucleophilic addition of living P2VP-Li+ chains onto the epoxy group of MPEO's. Finally, the hydroxy group formed at the junction of the MPEO and P2VP blocks was used to initiate the ring-opening polymerization of is an element of-caprolactone in the presence of tin octoate. The ABC starshaped triblocks were characterized by H-1 NMR spectroscopy and size exclusion chromatography. [less ▲] Detailed reference viewed: 26 (11 ULg) Synthesis of novel amphiphilic mikto-arm star-shaped copolymersRiva, Raphaël ; ; et alPoster (2009, December 14) Detailed reference viewed: 35 (7 ULg) Synthesis of novel block copolymers by cobalt-mediated radical polymerization (CMRP) and isoprene-assisted radical coupling reaction (I-ARC)Debuigne, Antoine ; Jérôme, Christine ; Detrembleur, Christophe ![]() Conference (2009, September 17) Nowadays, progresses in medicine, biotechnology, microelectronic and many other fields are more and more sustained by the development of novel polymer materials with constantly improved properties and ... [more ▼] Nowadays, progresses in medicine, biotechnology, microelectronic and many other fields are more and more sustained by the development of novel polymer materials with constantly improved properties and well-defined molecular parameters. In this context, we designed an innovative and very promising tool for macromolecular engineering. This technique, called Isoprene-Assisted Radical Coupling (I-ARC), allows to couple quantitatively polymer chains preformed by Cobalt-Mediated Radical Polymerization (CMRP), an efficient controlled radical polymerization system for vinyl acetate (VAc) and acrylonitrile (AN). Typically, addition of isoprene to well-defined polymers prepared by CMRP invariably leads to the quantitative coupling reaction of the chains, as assessed by the perfect doubling of the molar mass of the polymer. Importantly, the I-ARC reaction is not limited to macromolecules with low molar masses and homopolymers, contrary to the previously reported radical chains coupling methods. Indeed, when applied to diblock copolymers, I-ARC constitutes a straightforward approach for the synthesis of telechelic symmetrical ABA triblock copolymers, as illustrated by the preparation of poly(vinyl acetate)-b-poly(acrylonitrile)-b-poly(vinyl acetate) triblock copolymers and their derivatives. [less ▲] Detailed reference viewed: 19 (2 ULg) Synthesis of novel carbohydrate surfactants by combination of enzymatic catalysis and thiol-Michael additionBoyère, Cédric ; Favrelle, Audrey ; Broze, Guy et alPoster (2011, April 29) Detailed reference viewed: 29 (10 ULg) Synthesis of novel conjugated oligomers for second-order nonlinear optics: incorporation of a central spacer as a conjugation modulator; Dubois, Philippe ; Jérôme, Robert ![]() in Journal of the Chemical Society. Perkin Transactions (1997), 2(6), 1209-1216 A new series of second-order nonlinear optical chromophores has been synthesized that consists of a conjugated segment end-capped with an electron acceptor and an electron donor, respectively, and a ... [more ▼] A new series of second-order nonlinear optical chromophores has been synthesized that consists of a conjugated segment end-capped with an electron acceptor and an electron donor, respectively, and a central spacer intended to modulate the electro-optical effect. Conjugated chains have been tailored with trans-vinylene-1,5-thienylene as the building unit and N,N-dimethylamino and nitro groups as the donor–acceptor pair. Four spacers have been incorporated into the central part of the conjugated oligomers, which range from saturated to totally unsaturated functions, i.e. from methylene to vinylene units. The general strategy relies upon two consecutive Wittig or Wittig–Horner reactions between the spacer precursor and an aromatic phosphonium or phosphonate bearing the strong electron donor and the acceptor, respectively. Two synthetic pathways have been studied. The first procedure is based on the use of a symmetric precursor for the spacer. However, a reaction byproduct is formed, which must be removed and decreases the reaction efficiency. The second approach requires an asymmetric precursor for the spacer, the synthesis of which is a multistep process. In order to evaluate the effect of the spacer, a completely conjugated oligomer has been prepared by the one-step coupling of two conjugated segments end-functionalized by the electron donor and the acceptor, respectively. [less ▲] Detailed reference viewed: 22 (3 ULg) Synthesis of novel D-glucuronic acid fatty esters using Candida antarctica lipase in tert-butanol; Lognay, Georges ; Blecker, Christophe et alin Biotechnology Letters (2004), 26(5), 419-424 Glucuronic acid n-alkyl esters, a novel class of promising biosurfactants and their corresponding glucose esters with the same side-chain length, were synthesized by direct esterification in a non-aqueous ... [more ▼] Glucuronic acid n-alkyl esters, a novel class of promising biosurfactants and their corresponding glucose esters with the same side-chain length, were synthesized by direct esterification in a non-aqueous phase (tert-butanol) using an immobilized lipase. [less ▲] Detailed reference viewed: 16 (4 ULg) Synthesis of novel functional aliphatic polyestersSchmeits, Stephanie ; Riva, Raphaël ; Jérôme, Christine et alin Polymer Preprints (2008), 49(1), 222-223 Detailed reference viewed: 67 (34 ULg) Synthesis of novel functional aliphatic polyesters by association of ring-opening polymerization and click chemistryLecomte, Philippe ; Schmeits, Stephanie ; Riva, Raphaël et alConference (2008, April 09) Nowadays, biodegradable and biocompatible aliphatic polyesters are widely used as environmentally friendly thermoplastics and biomaterials. Nevertheless, the absence of any functional group along the ... [more ▼] Nowadays, biodegradable and biocompatible aliphatic polyesters are widely used as environmentally friendly thermoplastics and biomaterials. Nevertheless, the absence of any functional group along the chain is a severe limitation for the development of new applications. Very recently, it was reported by Emrick et al. and by us that copper(I)-mediated 1,3-dipolar Huisgen's cycloaddition of alkynes and azides, the most widely used “click” reaction in the frame of macromolecular engineering, is very efficient to derivatize aliphatic polyesters. Due to the tolerance for many functional groups, cumbersome protection and deprotection steps are not needed. One main advantage of copper(I)-mediated Huisgen's cycloaddition compared to other reactions previously used to derivatize aliphatic polyesters relies on the mildness of the experimental conditions, which results in limited degradation. Our most recent results dealing with the combination of “click” chemistry and ring-opening polymerization towards functional PCL and PLA, networks, graft and hyperbranched copolymers will be highlighted. [less ▲] Detailed reference viewed: 27 (9 ULg) Synthesis of novel functional PEO as builiding block for biomaterialsRieger, Jutta ; ; et alPoster (2005, June 01) Detailed reference viewed: 9 (2 ULg) Synthesis of novel poly(N-vinyl amide)s containing copolymers by cobalt-mediated radical polymerizationKermagoret, Anthony ; Hurtgen, Marie ; Liu, Ji et alPoster (2012, May 10) Poly(N-vinyl amide)s are found in many applications due to their valued properties including water solubility, biocompatibility, metal-coordination ability, etc. Although N-vinyl amides are easily ... [more ▼] Poly(N-vinyl amide)s are found in many applications due to their valued properties including water solubility, biocompatibility, metal-coordination ability, etc. Although N-vinyl amides are easily polymerized via radical pathways, their growing radicals are quite reactive due to the lack of stabilizing group, rendering the synthesis of well-defined poly(N-vinyl amide)s challenging. Thus, we explored the organometallic-mediated radical polymerization (OMRP) of a series of N-vinyl amides using bis(acetylacetonato)cobalt(II) as controlling agent in order to develop a platform for the precision synthesis of poly(N-vinyl amide)s. [less ▲] Detailed reference viewed: 35 (7 ULg) Synthesis of novel polybutadiene-graft-poly(sodium methacrylate) amphiphilic copolymers as precursors for liquid crystalline graft copolymers; ; et al in Macromolecular Chemistry and Physics (1999), 200(7), 1630-2638 Well-defined polybutadiene-graft-poly(tert-butyl methacrylate) (PBD-g-PtBMA) copolymers were prepared by reaction of PtBMA chains end-capped with a tert-butyl 4-vinylbenzoate (tBVB) anion, with the ... [more ▼] Well-defined polybutadiene-graft-poly(tert-butyl methacrylate) (PBD-g-PtBMA) copolymers were prepared by reaction of PtBMA chains end-capped with a tert-butyl 4-vinylbenzoate (tBVB) anion, with the selectively hydrosilylated 1,2-units of anionically synthesized PBD. Substitution of the tBVB anion for the anion of living PtBMA chains is required for the formation of the expected C-silylation product instead of the unstable O-silylation one. Subsequent hydrolysis of the poly(tert-butyl methacrylate) grafts followed by neutralization of the carboxylic acid groups by sodium hydroxide leads to amphiphilic polybuta-diene-graft-poly(sodium methacrylate) (PBD-g-PNaMA) graft copolymers. These copolymers form unimeric micelles in water, as observed by dynamic light scattering (DLS). Non-covalent liquid crystalline graft copo-lymers were prepared by cation exchange between PBD-g-PNaMA copolymers and an ammonium containing smectic mesogen. These copolymers form a smectic mesophase which is microphase separated from PBD. [less ▲] Detailed reference viewed: 44 (1 ULg) Synthesis of novel polymeric materials based on aliphatic polyesters by combination of different controlled polymerization methodsJérôme, Robert ; ; et alin Macromolecular Symposia (1998), 132 Combination of the living ring-opening polymerization (ROP) of ε-CL and lactides with the "controlled" free radical polymerization of styrene and methacrylic monomers is a versatile strategy for the ... [more ▼] Combination of the living ring-opening polymerization (ROP) of ε-CL and lactides with the "controlled" free radical polymerization of styrene and methacrylic monomers is a versatile strategy for the synthesis of well-defined block and graft copolymers. In this respect, the dual "living" polymerization strategy in which two different functional groups on a single molecule used to initiate the two controlled mechanisms is particularly efficient. Combination of ROP and step-growth polymerization is another versatile methodology for the preparation of a large variety of new materials, e.g. polyimide nanofbams, polyester/silica hybrid materials and star and branched polyesters by dendritic initiation. [less ▲] Detailed reference viewed: 37 (10 ULg) |
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