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However, despite formidable efforts, using acetonitrile as a Michael donor in these reactions has remained a significant challenge. Herein, we report a highly active manganese(I) complex [(PC<jats:sub>NHC<\/jats:sub>P)Mn(CO)<jats:sub>2<\/jats:sub>H] (<jats:bold>1<\/jats:bold>), which chemoselectively catalyzes the 1,4\u2010addition of unactivated nitriles (incl. acetonitrile) to \u03b1,\u03b2\u2010unsaturated ketones. The developed methodology operates under mild conditions, does not require any additives or bases, features low catalyst loadings (1\u2005mol\u2009%), fast reaction times (2\u20138\u2005hours), and is compatible with a wide variety of functional groups, including halides, trifluoromethyl, alkenyl, alkynyl, and (hetero)aryl groups. Extensive mechanistic studies revealed that after base\u2010free activation of the nitrile, either the N\u2010bound manganese\u2010ketenimine (propionitrile or benzyl cyanide) or the C\u2010bound manganese\u2010cyanoalkyl (acetonitrile) complex is formed. The difference in stability of these two species explains why more sterically hindered and presumably less activated nitriles (<jats:italic>i.e<\/jats:italic>., propionitrile, and butyronitrile) show higher reactivity than their corresponding more activated congeners (<jats:italic>i.e<\/jats:italic>., acetonitrile). Finally, the practicality of our approach was demonstrated through a gram\u2010scale reaction and subsequent derivatizations of the obtained product into important organic motifs such as ene\u2010lactams and tetrahydropyridines.<\/jats:p>","DOI":"10.1002\/anie.202423275","type":"journal-article","created":{"date-parts":[[2025,2,19]],"date-time":"2025-02-19T09:33:58Z","timestamp":1739957638000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Manganese\u2010Ketenimine Intermediates as Active Catalysts in the Michael Addition of Unactivated Nitriles to \u03b1,\u03b2\u2010Unsaturated Ketones"],"prefix":"10.1002","volume":"64","author":[{"given":"Kartick","family":"Dey","sequence":"first","affiliation":[{"name":"Schulich Faculty of Chemistry Technion \u2013 Israel Institute of Technology  Technion City 3200008 Haifa Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Akhanda","family":"Gorai","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry Technion \u2013 Israel Institute of Technology  Technion City 3200008 Haifa Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Katarzyna","family":"M\u0142odzikowska\u2010Pie\u0144ko","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry Technion \u2013 Israel Institute of Technology  Technion City 3200008 Haifa Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Natalia","family":"Fridman","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry Technion \u2013 Israel Institute of Technology  Technion City 3200008 Haifa Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Idan","family":"Avigdori","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry Technion \u2013 Israel Institute of Technology  Technion City 3200008 Haifa Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Renana","family":"Gershoni\u2010Poranne","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry Technion \u2013 Israel Institute of Technology  Technion City 3200008 Haifa Israel"},{"name":"The Resnick Sustainability Center for Catalysis Technion \u2013 Israel Institute of Technology  Technion City 3200008 Haifa Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6008-286X","authenticated-orcid":false,"given":"Graham","family":"de Ruiter","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry Technion \u2013 Israel Institute of Technology  Technion City 3200008 Haifa Israel"},{"name":"The Resnick Sustainability Center for Catalysis Technion \u2013 Israel Institute of Technology  Technion City 3200008 Haifa Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,3,25]]},"reference":[{"key":"e_1_2_9_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/a804370a"},{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/jm100762r"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.2165\/0003495-200868002-00002"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1007\/s12325-009-0030-9"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1517\/14656560903176446"},{"key":"e_1_2_9_6_1","volume-title":"The chemistry of the cyano group","author":"Rappoport Z.","year":"1970"},{"key":"e_1_2_9_7_1","unstructured":"A.\u2005J. 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