Hydroamination of acrylonitrile

Fig. 12) [91 ]. This phosphine-carbene ligand has been used in the nickel catalyzed hydroamination of acrylonitrile derivatives [92]. 

A nickel-catalyzed hydroamination of acrylonitrile using cationic pincer complexes has been described (Scheme 3-109). Mechanistic studies suggested that a simple Lewis acidic role of nickel may be responsible for the catalysis in this group... 

Related carbodiphosphoranes of Cu(I)- and Au(I)-t-butoxide complexes (47) have been prepared and rigorously characterized. Both complexes were explored for the anti-Markovnikov hydroamination of acrylonitrile with aniline (Scheme 15.59). The Cu(I) system provided higher conversions to product over the Au(I) complex, and under the reaction conditions explored, only the Cu catalyst yielded high conversions under an argon atmosphere [257]. 

Cationic Ni(II)-pincer complexes have also been exploited for the hydroamination of acrylonitrile with anihne [258]. Stoichiometric reactions in this case suggest that a Lewis acid mechanism promoting the anti-Markovnikov hydroamination is active (Figure 15.7) [258]. 

---