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For the ligands TMEDA and <jats:italic>t<\/jats:italic>BuBOX, the catalysis shows no unusual features and proceeds via [(N\uf8ffN)Zn(Et){OC(CF<jats:sub>3<\/jats:sub>)(Et)Ph}]. For N\uf8ffN\uf8fe<jats:bold>L<\/jats:bold>, the observation of autocatalytic asymmetric enhancement during the catalysis, and unusual inverse concentration dependence on the reaction rate, indicate the participation of an additional novel catalytic cycle that goes through a dinuclear intermediate containing one ZnEt<jats:sub>2<\/jats:sub> and one ZnEt fragment connected by N\uf8ffN and OR bridges. Interestingly, the <jats:sup>19<\/jats:sup>F NMR signals of the main product of the reaction ([Zn(Et){OC*(CF<jats:sub>3<\/jats:sub>)(Et)Ph}]<jats:sub>2<\/jats:sub>) allowed us to assess the enantioselectivity of the processes in situ without the assistance of chiral chromatography.<\/jats:p>","DOI":"10.1002\/chem.201403648","type":"journal-article","created":{"date-parts":[[2014,9,15]],"date-time":"2014-09-15T15:41:18Z","timestamp":1410795678000},"page":"14800-14806","source":"Crossref","is-referenced-by-count":13,"title":["Diamine\u2010Catalyzed Addition of ZnEt<sub>2<\/sub> to PhC(O)CF<sub>3<\/sub>: Two Mechanisms and Autocatalytic Asymmetric Enhancement"],"prefix":"10.1002","volume":"20","author":[{"given":"Mercedes","family":"Calvillo\u2010Barahona","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Juan A.","family":"Casares","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Carlos","family":"Cordovilla","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Miroslav N.","family":"Genov","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jes\u00fas M.","family":"Mart\u00ednez\u2010Ilarduya","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pablo","family":"Espinet","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2014,9,15]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo01261a013"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar9001763"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr1004293"},{"key":"e_1_2_6_5_2","unstructured":"\u00a0"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100166a"},{"key":"e_1_2_6_7_2","first-page":"1909","author":"Tur F.","year":"2010","journal-title":"Synthesis"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201109040"},{"key":"e_1_2_6_8_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201109040"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201201125"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/c3ob41888j"},{"key":"e_1_2_6_11_2","unstructured":"\u00a0"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/cen-v084n033.p015"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jfluchem.2006.01.011"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jfluchem.2006.05.006"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jfluchem.2006.06.007"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1131943"},{"key":"e_1_2_6_17_2","volume-title":"The Pesticide Manual: A World Compendium","year":"2012"},{"key":"e_1_2_6_18_2","unstructured":"\u00a0"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00013a004"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr000411y"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac200577122111"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.2174\/138527207779316453"},{"key":"e_1_2_6_23_2","first-page":"1647","author":"Hatano M.","year":"2008","journal-title":"Synthesis"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr078340r"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetasy.2009.03.015"},{"key":"e_1_2_6_26_2","first-page":"10","volume":"7","author":"Somanathan R.","year":"2010","journal-title":"Mini\u2010Rev. 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