{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T13:22:45Z","timestamp":1791292965802,"version":"4.1.0"},"reference-count":71,"publisher":"Wiley","issue":"16","license":[{"start":{"date-parts":[[2005,5,27]],"date-time":"2005-05-27T00:00:00Z","timestamp":1117152000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2005,8,5]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    The acetylation of\n                    <jats:italic>tert<\/jats:italic>\n                    \u2010butanol with acetic anhydride catalyzed by 4\u2010(dimethylamino)pyridine (DMAP) has been studied at the Becke3\u2009LYP\/6\u2010311+G(d,p)\/\/Becke3\u2009LYP\/6\u201031G(d) level of theory. Solvent effects have been estimated through single\u2010point calculations with the PCM\/UAHF solvation model. The energetically most favorable pathway proceeds through nucleophilic attack of DMAP at the anhydride carbonyl group and subsequent formation of the corresponding acetylpyridinium\/acetate ion pair. Reaction of this ion pair with the alcohol substrate yields the final product,\n                    <jats:italic>tert<\/jats:italic>\n                    \u2010butylacetate. The competing base\u2010catalyzed reaction pathway can either proceed in a concerted or in a stepwise manner. In both cases the reaction barrier far exceeds that of the nucleophilic catalysis mechanism. The reaction mechanism has also been studied experimentally in dichloromethane through analysis of the reaction kinetics for the acetylation of cyclohexanol with acetic anhydride, in the presence of DMAP as catalyst and triethylamine as the auxiliary base. The reaction is found to be first\u2010order with respect to acetic anhydride, cyclohexanol, and DMAP, and zero\u2010order with respect to triethyl amine. Both the theoretical as well as the experimental studies strongly support the nucleophilic catalysis pathway.\n                  <\/jats:p>","DOI":"10.1002\/chem.200500398","type":"journal-article","created":{"date-parts":[[2005,5,27]],"date-time":"2005-05-27T08:57:38Z","timestamp":1117184258000},"page":"4751-4757","source":"Crossref","is-referenced-by-count":309,"title":["The DMAP\u2010Catalyzed Acetylation of Alcohols\u2014A Mechanistic Study (DMAP=4\u2010(Dimethylamino)pyridine)"],"prefix":"10.1002","volume":"11","author":[{"given":"Shangjie","family":"Xu","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ingmar","family":"Held","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bernhard","family":"Kempf","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Herbert","family":"Mayr","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wolfgang","family":"Steglich","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hendrik","family":"Zipse","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2005,7,25]]},"reference":[{"key":"e_1_2_5_1_2","unstructured":"\u00a0"},{"key":"e_1_2_5_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19690812313"},{"key":"e_1_2_5_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.196909811"},{"key":"e_1_2_5_3_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1972-21955"},{"key":"e_1_2_5_4_2","first-page":"97","volume":"176","author":"Litvinenko L. 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