title: From the N-Heterocyclic Carbene-Catalyzed Conjugate Addition of Alcohols to the Controlled Polymerization of (Meth)acrylates.
abstract: Among various N-heterocyclic carbenes (NHCs) tested, only 1,3-bis(tert-butyl)imidazol-2-ylidene (NHC(tBu) ) proved to selectively promote the catalytic conjugate addition of alcohols onto (meth)acrylate substrates. This rather rare example of NHC-catalyzed 1,4-addition of alcohols was investigated as a simple means to trigger the polymerization of both methyl methacrylate and methyl acrylate (MMA and MA, respectively). Well-defined α-alkoxy poly(methyl (meth)acrylate) (PM(M)A) chains, the molar masses of which could be controlled by the initial [(meth)acrylate]0/[ROH]0 molar ratio, were ultimately obtained in N,N-dimethylformamide at 25 °C. A hydroxyl-terminated poly(ethylene oxide) (PEO-OH) macro-initiator was also employed to directly access PEO-b-PMMA amphiphilic block copolymers. Investigations into the reaction mechanism by DFT calculations revealed the occurrence of two competitive concerted pathways, involving either the activation of the alcohol or that of the monomer by NHC(tBu) .
authors.affiliation: CNRS/Univ. Bordeaux, LCPO, UMR 5629, 16 avenue Pey-Berland, 33607 Pessac cedex (France), Fax: (+33) 54-00-08-487.
authors.forename: Winnie Nzahou
authors.initials: WN
authors.lastname: Ottou
authors.affiliation: CNRS/Univ. Pau&des Pays de l'Adour, IPREM, UMR 5254, 2 Avenue du Président P. Angot, 64053 Pau cedex 09 (France), Fax: (+33) 59-40-78-62.
authors.forename: Damien
authors.initials: D
authors.lastname: Bourichon
authors.affiliation: CNRS/Univ. Bordeaux, LCPO, UMR 5629, 16 avenue Pey-Berland, 33607 Pessac cedex (France), Fax: (+33) 54-00-08-487.
authors.forename: Joan
authors.initials: J
authors.lastname: Vignolle
authors.affiliation: CNRS/Univ. Bordeaux, LCPO, UMR 5629, 16 avenue Pey-Berland, 33607 Pessac cedex (France), Fax: (+33) 54-00-08-487.
authors.forename: Anne-Laure
authors.initials: AL
authors.lastname: Wirotius
authors.affiliation: CNRS/Univ. Bordeaux, ISM, UMR 5255, 351 cours de la Libération, 33400 Talence (France), Fax: (+33) 54-00-06-286.
authors.forename: Fredéric
authors.initials: F
authors.lastname: Robert
authors.affiliation: CNRS/Univ. Bordeaux, ISM, UMR 5255, 351 cours de la Libération, 33400 Talence (France), Fax: (+33) 54-00-06-286.
authors.forename: Yannick
authors.initials: Y
authors.lastname: Landais
authors.affiliation: CNRS/Univ. Pau&des Pays de l'Adour, IPREM, UMR 5254, 2 Avenue du Président P. Angot, 64053 Pau cedex 09 (France), Fax: (+33) 59-40-78-62.
authors.forename: Jean-Marc
authors.initials: JM
authors.lastname: Sotiropoulos
authors.affiliation: CNRS/Univ. Pau&des Pays de l'Adour, IPREM, UMR 5254, 2 Avenue du Président P. Angot, 64053 Pau cedex 09 (France), Fax: (+33) 59-40-78-62. karinne.miqueu@univ-pau.fr.
authors.forename: Karinne
authors.initials: K
authors.lastname: Miqueu
authors.affiliation: CNRS/Univ. Bordeaux, LCPO, UMR 5629, 16 avenue Pey-Berland, 33607 Pessac cedex (France), Fax: (+33) 54-00-08-487. taton@enscbp.fr.
authors.forename: Daniel
authors.initials: D
authors.lastname: Taton
keywords: N-heterocyclic carbenes; density functional calculations; organocatalysis; polymerization; reaction mechanisms