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The computational data has allowed us to rationalize the experimental outcome, validating some of the mechanistic steps proposed in the literature, as well as to propose new ones that considerably change and improve our understanding of the full reaction path (see scheme).<jats:boxed-text content-type=\"graphic\" position=\"anchor\"><jats:graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" mimetype=\"image\/gif\" position=\"anchor\" specific-use=\"enlarged-web-image\" xlink:href=\"graphic\/mcontent.gif\"><jats:alt-text>magnified image<\/jats:alt-text><\/jats:graphic><\/jats:boxed-text><\/jats:p><jats:p>The mechanisms of proline\u2010catalyzed and imidazole\u2010co\u2010catalyzed intramolecular Baylis\u2013Hillman reactions have been studied by using density functional theory methods at the B3LYP\/6\u201031G(d,p) level of theory. A polarizable continuum model (PCM B3LYP\/6\u201031++G(d,p)\/\/B3LYP\/6\u201031G(d,p)) was used to describe solvent effects. Different reaction pathways were investigated, which indicated that water is an important catalyst in the imine\/enamine conversion step in the absence of imidazole. When imidazole is used as a co\u2010catalyst, water is still important in the imidazole addition step, but is not present in the Baylis\u2013Hillman cyclization step. The computational data has allowed us to rationalize the experimental outcome of the intramolecular Baylis\u2013Hillman reaction, validating some of the mechanistic steps proposed in the literature, as well as to propose new ones that considerably change and improve our understanding of the full reaction path.<\/jats:p>","DOI":"10.1002\/chem.200801624","type":"journal-article","created":{"date-parts":[[2009,1,2]],"date-time":"2009-01-02T14:12:29Z","timestamp":1230905549000},"page":"1734-1746","source":"Crossref","is-referenced-by-count":32,"title":["Density Functional Study of Proline\u2010Catalyzed Intramolecular Baylis\u2013Hillman Reactions"],"prefix":"10.1002","volume":"15","author":[{"given":"Filipe\u2005J.\u2005S.","family":"Duarte","sequence":"first","affiliation":[]},{"given":"Eurico\u2005J.","family":"Cabrita","sequence":"additional","affiliation":[]},{"given":"Gernot","family":"Frenking","sequence":"additional","affiliation":[]},{"given":"A.\u2005Gil","family":"Santos","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2009,1,26]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/3527604677"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar0300468"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac200577071277"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/b415217b"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200400650"},{"key":"e_1_2_6_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200400650"},{"key":"e_1_2_6_7_2","doi-asserted-by":"crossref","first-page":"41","DOI":"10.1021\/cen-v082n036.p041","volume":"82","author":"Rouhi A. 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