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We describe an unusual, yet simple, Cu<jats:sup>II<\/jats:sup>\u2010catalyzed system for the amination of aryl chlorides in pure aqueous ammonia with 2.5\u2005mol\u2009% catalyst loading under non\u2010inert conditions. Different from previous systems, the reaction proceeds even without an additional organic solvent. Copper(II) sulfate in combination with 4,7\u2010dimethoxy\u20101,10\u2010phenanthroline enabled the amination of several aryl chlorides containing electron\u2010neutral, \u2010donating and \u2010withdrawing groups to the corresponding anilines with good to excellent yields. The upscaling potential of the procedure has been shown by the synthesis at 50\u2005mmol scale. The reaction proceeds as one of the rare cases of a Cu<jats:sup>II<\/jats:sup>\u2010assisted coupling, in contrast to the typical Cu<jats:sup>I<\/jats:sup>\u2212Cu<jats:sup>III<\/jats:sup> intermediates postulated for most Ullmann\u2010type coupling reactions. The copper(II) center allows for a nucleophilic substitution pathway, enabled by the deprotonation of coordinated ammonia.<\/jats:p>","DOI":"10.1002\/chem.202403023","type":"journal-article","created":{"date-parts":[[2024,8,22]],"date-time":"2024-08-22T16:11:12Z","timestamp":1724343072000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Copper(II)\u2010Catalyzed Amination of Aryl Chlorides in Aqueous Ammonia"],"prefix":"10.1002","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0322-0557","authenticated-orcid":false,"given":"Lucas S.","family":"Mello","sequence":"first","affiliation":[{"name":"Catalysis Research Laboratory (CaRLa)  Im Neuenheimer Feld 584 69120 Heidelberg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Philipp D.","family":"Engel","sequence":"additional","affiliation":[{"name":"Catalysis Research Laboratory (CaRLa)  Im Neuenheimer Feld 584 69120 Heidelberg Germany"},{"name":"BASF SE  Carl-Bosch-Str. 38 67056 Ludwigshafen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Patrizio","family":"Orecchia","sequence":"additional","affiliation":[{"name":"Catalysis Research Laboratory (CaRLa)  Im Neuenheimer Feld 584 69120 Heidelberg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Katharina","family":"Bleher","sequence":"additional","affiliation":[{"name":"Anorganisch-Chemisches Institut and IWR Universit\u00e4t Heidelberg  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Frank","family":"Rominger","sequence":"additional","affiliation":[{"name":"Organisch-Chemisches Institut  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kailaskumar","family":"Borate","sequence":"additional","affiliation":[{"name":"BASF Chemicals India Pvt. 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Thane Belapur Road Navi Mumbai 400705 India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Roland","family":"Goetz","sequence":"additional","affiliation":[{"name":"BASF SE  Carl-Bosch-Str. 38 67056 Ludwigshafen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Peter","family":"Deglmann","sequence":"additional","affiliation":[{"name":"BASF SE  Carl-Bosch-Str. 38 67056 Ludwigshafen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ansgar","family":"Sch\u00e4fer","sequence":"additional","affiliation":[{"name":"BASF SE  Carl-Bosch-Str. 38 67056 Ludwigshafen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Christian","family":"Winter","sequence":"additional","affiliation":[{"name":"BASF SE  Carl-Bosch-Str. 38 67056 Ludwigshafen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Michael","family":"Rack","sequence":"additional","affiliation":[{"name":"BASF SE  Carl-Bosch-Str. 38 67056 Ludwigshafen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Peter","family":"Comba","sequence":"additional","affiliation":[{"name":"Catalysis Research Laboratory (CaRLa)  Im Neuenheimer Feld 584 69120 Heidelberg Germany"},{"name":"Anorganisch-Chemisches Institut and IWR Universit\u00e4t Heidelberg  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"A. Stephen K.","family":"Hashmi","sequence":"additional","affiliation":[{"name":"Catalysis Research Laboratory (CaRLa)  Im Neuenheimer Feld 584 69120 Heidelberg Germany"},{"name":"Organisch-Chemisches Institut  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2332-0376","authenticated-orcid":false,"given":"Thomas","family":"Schaub","sequence":"additional","affiliation":[{"name":"Catalysis Research Laboratory (CaRLa)  Im Neuenheimer Feld 584 69120 Heidelberg Germany"},{"name":"BASF SE  Carl-Bosch-Str. 38 67056 Ludwigshafen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,10,16]]},"reference":[{"key":"e_1_2_8_1_1","unstructured":"\u00a0"},{"key":"e_1_2_8_2_2","first-page":"703","volume-title":"Amines, Aromatic. in Ullmann's Encyclopedia of Industrial Chemistry","author":"Vogt P. 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