Soft Molecular Activation Research Center (SMARC), Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan.
Molecular Chirality Research Center (MCRC), Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan.
Sci Rep. 2018 Jan 16;8(1):837. doi: 10.1038/s41598-018-19178-4.
A phosphoiminoBINOL ligand was designed to form a dinuclear metal complex that could hold a malononitrile molecule. The dinuclear bis(phosphoimino)binaphthoxy-Pd(OAc) 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.
设计了一种膦亚氨基联萘配体，以形成能够容纳丙二腈分子的双核金属配合物。双核双（膦亚氨基）联萘氧钯（OAc）配合物催化 N-Boc-亚胺与丙二腈的双重曼尼希反应，以高对映选择性得到手性 1,3-二胺。这种合理的不对称催化剂在避免逆反应的同时，将第一个偶联产物顺利引入第二个偶联反应中，促进了过度反应向生产性反应过程的转化。
