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The reactivity of this SR\u2010protected 1,4\u2010benzoquinone has been compared with the behavior of the analogous OR\u2010protected acetal in copper\u2010catalyzed additions of ZnMe<jats:sub>2<\/jats:sub> by using chiral phosphoramidite ligands. The activation energy for 1,4\u2010methylation of the latter OR\u2010acetals with ZnMe<jats:sub>2<\/jats:sub> (&gt;95\u2009%\u2005<jats:italic>ee<\/jats:italic>) has been determined for two CuX<jats:sub>2<\/jats:sub> pre\u2010catalysts (X=OAc, 12.2\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>; X=OTf, 6.7\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>; Tf=triflate). The dithioacetal SR aromatizes in the presence of Cu<jats:sup>I<\/jats:sup>\/ZnMe<jats:sub>2<\/jats:sub> giving 1,4\u2010HOC<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>S(CH<jats:sub>2<\/jats:sub>)<jats:sub>3<\/jats:sub>SMe through C\uf8ffS bond formation. The disparate behavior of these two very closely related substrates is in accordance with the formation of closely related cuprate intermediates that were optimized by DFT calculations, supporting the synthetic and kinetic studies and thus defining the mechanisms of both pathways.<\/jats:p>","DOI":"10.1002\/chem.200903310","type":"journal-article","created":{"date-parts":[[2010,4,13]],"date-time":"2010-04-13T14:36:08Z","timestamp":1271169368000},"page":"5620-5629","source":"Crossref","is-referenced-by-count":20,"title":["Chemoselectivity as a Delineator of Cuprate Structure in Catalytic 1,4\u2010Addition of Diorganozinc Reagents to Michael Acceptors"],"prefix":"10.1002","volume":"16","author":[{"given":"Matthias","family":"Welker","sequence":"first","affiliation":[]},{"given":"Simon","family":"Woodward","sequence":"additional","affiliation":[]},{"given":"Luis\u2005F.","family":"Veiros","sequence":"additional","affiliation":[]},{"given":"Maria\u2005Jos\u00e9","family":"Calhorda","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2010,5,7]]},"reference":[{"key":"e_1_2_7_1_2","doi-asserted-by":"publisher","DOI":"10.1039\/b002690p"},{"key":"e_1_2_7_2_2","unstructured":"\u00a0"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja067533d"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/b717290g"},{"key":"e_1_2_7_5_2","unstructured":"\u00a0"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/3527600086.ch10"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/asia.200600034"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja049401v"},{"key":"e_1_2_7_9_2","unstructured":"\u00a0"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja8041433"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr800286r"},{"key":"e_1_2_7_12_2","volume-title":"The Chemistry of Organocopper Compounds","author":"Gartner T.","year":"2009"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19951071004"},{"key":"e_1_2_7_13_3","first-page":"1059","volume":"42","year":"1995","journal-title":"Angew. 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