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The solvent effect of dichloromethane was taken into account through PCM\/SCRF single\u2010point calculations at the B3LYP\/6\u201331G(d) level of theory. In marked contrast with that predicted for the reaction of alcohols with acetic anhydride, the mechanism in which nucleophilic activation of the monomer involving acylpyridinium intermediates was found to be energetically less favorable than the base activation of the alcohol through hydrogen bonding. The concerted pathway for the ring\u2010opening of lactide and lacOCA was shown to compete with the traditional stepwise mechanism involving tetrahedral intermediates. Furthermore, DMAP is proposed to act as a bifunctional catalyst through its basic nitrogen center and an acidic <jats:italic>ortho<\/jats:italic>\u2010hydrogen atom.<\/jats:p>","DOI":"10.1002\/chem.200800346","type":"journal-article","created":{"date-parts":[[2008,4,30]],"date-time":"2008-04-30T06:23:14Z","timestamp":1209536594000},"page":"5304-5312","source":"Crossref","is-referenced-by-count":112,"title":["Monomer versus Alcohol Activation in the 4\u2010Dimethylaminopyridine\u2010Catalyzed Ring\u2010Opening Polymerization of Lactide and Lactic <i>O<\/i>\u2010Carboxylic Anhydride"],"prefix":"10.1002","volume":"14","author":[{"given":"Colin","family":"Bonduelle","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Blanca","family":"Mart\u00edn\u2010Vaca","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fernando\u2005P.","family":"Coss\u00edo","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Didier","family":"Bourissou","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2008,5,29]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For general reviews of the applications of PLAs 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see:"},{"key":"e_1_2_6_80_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0267627"},{"key":"e_1_2_6_81_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo030156s"},{"key":"e_1_2_6_82_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp054048g"},{"key":"e_1_2_6_83_2","unstructured":"The terms \u201cbasic route\u201d and \u201cbase\u2010catalyzed mechanism\u201d refer to the ability of DMAP to activate the initiating\/propagating alcohol through N\u22c5\u22c5\u22c5H\uf8ffO hydrogen bonding and to transfer the labile proton back to the exocyclic oxygen atom of the monomer."},{"key":"e_1_2_6_84_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar00167a003"},{"key":"e_1_2_6_85_2","unstructured":"For experimental and computational studies on the hydrolysis and alcoholysis of carboxylic esters and formates see:"},{"key":"e_1_2_6_86_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00255a021"},{"key":"e_1_2_6_87_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00189a045"},{"key":"e_1_2_6_88_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00010a040"},{"key":"e_1_2_6_89_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00042a057"},{"key":"e_1_2_6_90_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00067a008"},{"key":"e_1_2_6_91_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo061165e"},{"key":"e_1_2_6_92_2","unstructured":"For experimental and theoretical studies on the aminolysis of carboxylic esters and formates see:"},{"key":"e_1_2_6_93_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00387a001"},{"key":"e_1_2_6_94_2","doi-asserted-by":"publisher","DOI":"10.1002\/jlac.199619961003"},{"key":"e_1_2_6_95_2","first-page":"1511","author":"Wang L.","year":"1996","journal-title":"Liebigs Ann."},{"key":"e_1_2_6_96_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol006691l"},{"key":"e_1_2_6_97_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo0263723"},{"key":"e_1_2_6_98_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0536403"},{"key":"e_1_2_6_99_2","unstructured":"\u03b1\u2010Lactones are elusive intermediates; 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