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Reactions proceeded readily at 120 \u00b0C in the absence of solvent to give selective anti\u2010Markovnikov addition. Slow addition was observed at 25 \u00b0C with either electron\u2010deficient <jats:italic>p<\/jats:italic>\u2010chlorostyrene or secondary cyclic amines such as pyrrolidine, piperidine, or morpholine. Primary amines were prone to a second hydroamination reaction to form tertiary amine byproducts. The selectivity for the mono(hydroamination) products could be improved with a two\u2010fold excess of the amine. KN(SiMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub> showed higher catalytic activity but lower selectivity in comparison to that of LiN(SiMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>, resulting in undesired C\u2013H\u2010activation byproducts. The mechanism of the lithium\u2010catalyzed hydroamination and the influence of TMEDA was studied with density functional theory. (\u00a9 Wiley\u2010VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2007)<\/jats:p>","DOI":"10.1002\/ejoc.200700147","type":"journal-article","created":{"date-parts":[[2007,5,10]],"date-time":"2007-05-10T08:49:49Z","timestamp":1178786989000},"page":"3311-3325","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":88,"title":["Base\u2010Catalyzed Anti\u2010Markovnikov Hydroamination of Vinylarenes \u2013 Scope, Limitations and Computational Studies"],"prefix":"10.1002","volume":"2007","author":[{"given":"Patricia","family":"Horrillo\u2010Mart\u00ednez","sequence":"first","affiliation":[]},{"given":"Kai C.","family":"Hultzsch","sequence":"additional","affiliation":[]},{"given":"Adri\u00e0","family":"Gil","sequence":"additional","affiliation":[]},{"given":"Vicen\u00e7","family":"Branchadell","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2007,6,22]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/zfch.19860261002"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/9783527619351"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr960433d"},{"key":"e_1_2_6_5_2","volume-title":"Transition Metals for Organic Synthesis","author":"M\u00fcller T. 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