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Dinuclear PhosphoiminoBINOL-Pd Container for Malononitrile: Catalytic Asymmetric Double Mannich Reaction for Chiral
Takayoshi Arai1,2,3, Katsuya Sato4,5,6, Ayu Nakamura4,5,6
1Soft Molecular Activation Research Center (SMARC), Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan. tarai@faculty.chiba-u.jp.
Abstract:
A phosphoiminoBINOL ligand was designed to form a dinuclear metal complex that could hold a malononitrile molecule. The dinuclear bis(phosphoimino)binaphthoxy-Pd2(OAc)2 complex catalyzed a double Mannich reaction of N-Boc-imines with malononitrile to give chiral 1,3-diamines with high enantioselectivity. The rational asymmetric catalyst, which smoothly introduces the first coupling product to the second coupling reaction while avoiding the reverse reaction, facilitates the over-reaction into a productive reaction process.
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