Imidazol(in)ium Hydrogen Carbonates as a Genuine Source of N-Heterocyclic Carbenes (NHCs): Applications to the Facile Preparation of NHC Metal Complexes and to NHC-Organocatalyzed Molecular and

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• 作者：Mar茅va F猫vre ; Julien Pinaud ; Alexandre Leteneur ; Yves Gnanou ; Joan Vignolle ; Daniel Taton ; Karinne Miqueu ; Jean-Marc Sotiropoulos
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：April 18, 2012
• 年：2012
• 卷：134
• 期：15
• 页码：6776-6784
• 全文大小：515K
• 年卷期：v.134,no.15(April 18, 2012)
• ISSN：1520-5126

文摘

Anion metathesis of imidazol(in)ium chlorides with KHCO₃ afforded an easy one step access to air stable imidazol(in)ium hydrogen carbonates, denoted as [NHC(H)][HCO₃]. In solution, these compounds were found to be in equilibrium with their corresponding imidazol(in)ium carboxylates, referred to as N-heterocyclic carbene (NHC)-CO₂ adducts. The [NHC(H)][HCO₃] salts were next shown to behave as masked NHCs, allowing for the NHC moiety to be readily transferred to both organic and organometallic substrates, without the need for dry and oxygen-free conditions. In addition, such [NHC(H)][HCO₃] precursors were successfully investigated as precatalysts in two selected organocatalyzed reactions of molecular chemistry and polymer synthesis, namely, the benzoin condensation reaction and the ring-opening polymerization of d,l-lactide, respectively. The generation of NHCs from [NHC(H)][HCO₃] precursors occurred via the formal loss of H₂CO₃via a concerted low energy pathway, as substantiated by Density Functional Theory (DFT) calculations.