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Experimental parameters were optimized to afford full conversions and high yields of \u03b3\u2010aminoformamides starting from twelve symmetrical substrates with alkyl or aryl substituents on their nitrogen atoms, and five unsymmetrical 1\u2010alkyl\u20103\u2010arylimidazolinium chlorides. NMR and XRD analyses showed that the cleavage of unsymmetrical salts led to \u03b3\u2010alkylamino\u2010<jats:italic>N<\/jats:italic>\u2010arylformamides with a high regioselectivity and that bulky alkyl or aryl groups on the formamide moiety led to the isolation of the (<jats:italic>E<\/jats:italic>)\u2010isomer in high stereoisomeric purity (&gt;95\u2009%), whereas smaller and more flexible alkyl substituents afforded mixtures of (<jats:italic>E<\/jats:italic>)\u2010 and (<jats:italic>Z<\/jats:italic>)\u2010rotamers. Control experiments showed that the hydrolysis of 1,3\u2010dimesitylimidazolinium chloride (SIMes\u2009\u22c5\u2009HCl) did not occur readily in pure or acidic water and that the presence of bulky aromatic substituents on the nitrogen atoms of 1,3\u2010bis(2,6\u2010diisopropylphenyl)imidazolinium chloride (SIDip\u2009\u22c5\u2009HCl) efficiently slowed down its hydrolysis under basic aqueous conditions. Most strikingly, this work highlighted the critical influence of the counteranion on the reactivity of imidazolinium cations. Indeed, the chloride salts underwent a facile hydrolysis in the presence of water and Na<jats:sub>2<\/jats:sub>CO<jats:sub>3<\/jats:sub>, whereas various other NHC\u2009\u22c5\u2009HX derivatives reacted much slower or remained essentially inert under these conditions.<\/jats:p>","DOI":"10.1002\/chem.202302402","type":"journal-article","created":{"date-parts":[[2023,9,4]],"date-time":"2023-09-04T09:30:02Z","timestamp":1693819802000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["The Facile Hydrolysis of Imidazolinium Chlorides (N\u2010Heterocyclic Carbene Precursors) Under Basic Aqueous Conditions"],"prefix":"10.1002","volume":"29","author":[{"given":"Nedra","family":"Touj","sequence":"first","affiliation":[{"name":"Laboratory of Catalysis MolSys Research Unit Universit\u00e9 de Li\u00e8ge Institut de Chimie Organique (B6a)  All\u00e9e du six Ao\u00fbt 13 4000 Li\u00e8ge Belgium"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jerwin Jay","family":"Taping","sequence":"additional","affiliation":[{"name":"Laboratory of Catalysis MolSys Research Unit Universit\u00e9 de Li\u00e8ge Institut de Chimie Organique (B6a)  All\u00e9e du six Ao\u00fbt 13 4000 Li\u00e8ge Belgium"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Nikolay","family":"Tumanov","sequence":"additional","affiliation":[{"name":"Department of Chemistry Namur Institute of Structured Matter (NISM) Universit\u00e9 de Namur  Rue de Bruxelles 61 5000 Namur Belgium"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Johan","family":"Wouters","sequence":"additional","affiliation":[{"name":"Department of Chemistry Namur Institute of Structured Matter (NISM) Universit\u00e9 de Namur  Rue de Bruxelles 61 5000 Namur Belgium"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1134-2992","authenticated-orcid":false,"given":"Lionel","family":"Delaude","sequence":"additional","affiliation":[{"name":"Laboratory of Catalysis MolSys Research Unit Universit\u00e9 de Li\u00e8ge Institut de Chimie Organique (B6a)  All\u00e9e du six Ao\u00fbt 13 4000 Li\u00e8ge Belgium"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2023,10,17]]},"reference":[{"key":"e_1_2_9_1_1","unstructured":"\u00a0"},{"key":"e_1_2_9_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/9783527671229"},{"volume-title":"N-Heterocyclic Carbenes: From Laboratory Curiosities to Efficient Synthetic Tools","year":"2017","author":"D\u00edez-Gonz\u00e1lez S.","key":"e_1_2_9_3_2"},{"volume-title":"N-Heterocyclic Carbenes in Catalytic Organic Synthesis","year":"2017","author":"Nolan S. 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