Details

Autor(en) / Beteiligte

• Merschel, Arne
• Vishnevskiy, Yury V.
• Neumann, Beate
• Stammler, Hans‐Georg
• Ghadwal, Rajendra S.

Titel

Ring‐Opening of 1,3‐Imidazole Based Mesoionic Carbenes (iMICs) and Ring‐Closing Clicks: Facile Access to iMIC‐Compounds

Ist Teil von

• Chemistry : a European journal, 2024-01, Vol.30 (3), p.e202303652-n/a

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2024

Link zum Volltext

Quelle

Wiley Online Library - AutoHoldings Journals

Beschreibungen/Notizen

• Herein, ring‐opening of mesoionic carbenes (iMICs) (iMIC=[ArC{N(Dipp)}2C(SiMe3)C:) (Dipp=2,6‐iPr2C6H3, Ar=Ph, 4‐Me2NC6H4 or 4‐PhC6H4) based on an 1,3‐imidazole scaffold to yield N‐ethynylformimidamide (eFIM) derivatives as crystalline solids (eFIM={(Dipp)N=C(Ar)N(Dipp)}C≡CSiMe3) is reported. eFIMs are thermally stable under inert gas atmosphere and show moderate air stability (t1/2=3 h for Ar=Ph). eFIMs are excellent surrogates of iMICs, which generally have a limited shelf‐life, and readily undergo ring‐closing click reactions with a variety of main‐group as well as transition metal Lewis acids to form hitherto challenging iMIC‐compounds in good to excellent yields. In addition to the relevance of eFIMs in the synthesis of iMIC‐compounds, quantification of the stereoelectronic properties of a representative iMIC (Ar=Ph) by experimental and theoretical methods suggests remarkably σ‐donor property and steric profile of these new ligand sets. Stable unmasked iMICs are extremely scarce and have limited shelf‐life. An unprecedented ring‐opening of iMICs to N‐ethynylformimidamides (eFIMs) has been reported. eFIMs are thermally stable under an inert atmosphere and show moderately air‐stability. They are excellent iMIC‐surrogates and readily undergo ring‐closing‐clicks with a variety of (non)metal Lewis acids, affording iMIC‐compounds (iMIC)[M] with zero waste and easy workup.