Hyodo K, Nakamura S, * Shibata N. * Nagoya Institute of Technology, Japan
Enantioselective Aza-Morita–Baylis–Hillman Reactions of Acrylonitrile Catalyzed by
Palladium(II) Pincer Complexes having
C
2-Symmetric Chiral Bis(imidazoline) Ligands.
Angew. Chem. Int. Ed. 2012;
51: 10337-10341
Key words
palladium - bis(imidazoline) ligands - aza-Morita–Baylis–Hillman reaction
Significance
This paper describes the palladium-catalyzed enantioselective aza-Morita–Baylis–Hillman
reaction of acrylonitriles with imines. The bulky pincer ligand enabled the synthesis
of enantioenriched α-methylene-β-aminonitriles in high yield.
Comment
The palladium–pincer complex preferably activates acrylonitrile, even in the presence
of ethyl acrylate. The palladium ketenimide is a key intermediate for the asymmetric
induction. The palladium complex may promote other Lewis acid catalyzed reactions.
