Realizing 1,1‐Dehydration of Secondary Alcohols to Carbenes: Pyrrolidin‐2‐ols as a Source of Cyclic (Alkyl)(Amino)Carbenes

Herein we report secondary pyrrolidin‐2‐ols as a source of cyclic (alkyl)(amino)carbenes (CAAC) for the synthesis of CAAC‐CuI‐complexes and cyclic thiones when reacted with CuI‐salts and elemental sulfur, respectively, under reductive elimination of water from the carbon(IV)‐center. This result demo...

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Published in:Angewandte Chemie International Edition 2022-07, Vol.61 (28), p.e202202637-n/a
Main Authors: Das, Ayan, Elvers, Benedict J., Nayak, Mithilesh Kumar, Chrysochos, Nicolas, Anga, Srinivas, Kumar, Amar, Rao, D. Krishna, Narayanan, Tharangattu N., Schulzke, Carola, Yildiz, Cem B., Jana, Anukul
Format: Article
Language:English
Subjects:
1,1-Dehydration
Alcohols
Carbenes
Carbon
Catalysts
Coordination compounds
COVID-19
Dehydration
Dehydrogenation
Elimination
Hydrated Carbenes
Hydrogen bonds
Metal complexes
Salts
Sulfur
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Summary:Herein we report secondary pyrrolidin‐2‐ols as a source of cyclic (alkyl)(amino)carbenes (CAAC) for the synthesis of CAAC‐CuI‐complexes and cyclic thiones when reacted with CuI‐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 CuI‐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. The thermal dehydration of secondary alcohols to carbenes and reverse back‐hydration are showcased. The in situ generation of cyclic (alkyl)(amino)carbenes through the thermal 1,1‐dehydration of secondary pyrrolidin‐2‐ol alcohols was realized and utilized for various purposes such as the synthesis of transition metal‐carbene complexes. This methodology opens a door for further consideration of various secondary alcohols as sources of carbenes.
ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202202637