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 Ca2+. The role of the metal was evaluated by a study using the metal‐free catalysts: [Ph2N−][Me4N+] and [Ph3C−][Me4N+]. These “naked” amides and carbanions can act as catalysts in the conversion of activated double bonds (C-O and C-N) in the hydroamination of Ar-N-C-O and R-N-C-N-R (R=alkyl) by Ph2NH. For the intramolecular hydroamination of unactivated CC bonds in H2C-CHCH2CPh2CH2NH2 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.