2014/11/05 by Johanne Penafiel, Laurent Maron, Sjoerd Harder · 1 citation
Chemistry · #Organoboron and organosilicon chemistry #Asymmetric Hydrogenation and Catalysis #Organometallic Complex Synthesis and Catalysis
paper · doi:10.1002/anie.201408814
openalex publication_date 2014/11/05 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/01
Organocalcium compounds have been reported as efficient catalysts for various alkene transformations. In contrast to transition metal catalysis, the alkenes are not activated by metal-alkene orbital interactions. Instead it is proposed that alkene activation proceeds through an electrostatic interaction with a Lewis acidic Ca(2+) . The role of the metal was evaluated by a study using the metal-free catalysts: [Ph2 N(-) ][Me4 N(+) ] and [Ph3 C(-) ][Me4 N(+) ]. These "naked" amides and carbanions can act as catalysts in the conversion of activated double bonds (CO and CN) in the hydroamination of ArNCO and RNCNR (R=alkyl) by Ph2 NH. For the intramolecular hydroamination of unactivated CC bonds in H2 CCHCH2 CPh2 CH2 NH2 the presence of a metal cation is crucial. A new type of hybrid catalyst consisting of a strong organic Schwesinger base and a simple metal salt can act as catalyst for the intramolecular alkene hydroamination. The influence of the cation in catalysis is further evaluated by a DFT study.