Daş, AyanElvers, Benedict J.Nayak, Mithilesh KumarChrysochos, NicolasAnga, SrinivasKumar, AmarRao, D. KrishnaNarayanan, Tharangattu N.Schulzke, CarolaYıldız, Cem BurakJana, Anukul2022-05-232022-05-2320221433-78511521-3773https:/dx.doi.org/10.1002/anie.202202637https://hdl.handle.net/20.500.12451/9414Herein we report secondary pyrrolidin-2-ols as a source of cyclic (alkyl)(amino)carbenes (CAAC) for the synthesis of CAAC-Cu-I-complexes and cyclic thiones when reacted with Cu-I-salts and elemental sulfur, respectively, under reductive elimination of water from the carbon(IV)-center. This result demonstrates a convenient and facile access to CAAC-based Cu-I-salts, which are well known catalysts for different organic transformations. It further establishes secondary alcohols to be a viable source of carbenes-realizing after 185 years Dumas' dream who tried to prepare the parent carbene (CH2) by 1,1-dehydration of methanol. Addressed is also the reactivity of water towards CAACs, which proceeds through an oxidative addition of the O-H bond to the carbon(II)-center. This emphasizes the ability of carbon-compounds to mimic the reactivity of transition-metal complexes: reversible oxidative addition and reductive elimination of the O-H bond to/from the C(II)/C(IV)-centre.eninfo:eu-repo/semantics/embargoedAccess1-DehydrationCarbenesDehydrogenationEliminationHydrated CarbenesArticle----10.1002/anie.20220263735362643Q1WOS:000791488500001Q1