Dinuclear PhosphoiminoBINOL-Pd Container for Malononitrile: Catalytic Asymmetric Double Mannich Reaction for Chiral 1,3-Diamine Synthesis

Takayoshi Arai; Katsuya Sato; Ayu Nakamura; Hiroki Makino; Hyuma Masu

doi:10.1038/s41598-018-19178-4

Dinuclear PhosphoiminoBINOL-Pd Container for Malononitrile: Catalytic Asymmetric Double Mannich Reaction for Chiral 1,3-Diamine Synthesis

Sci Rep. 2018 Jan 16;8(1):837. doi: 10.1038/s41598-018-19178-4.

Authors

Takayoshi Arai^{1

2

3}, Katsuya Sato^{4

5

6}, Ayu Nakamura^{4

5

6}, Hiroki Makino^{4

5

6}, Hyuma Masu⁷

Affiliations

¹ Soft Molecular Activation Research Center (SMARC), Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan. tarai@faculty.chiba-u.jp.
² Molecular Chirality Research Center (MCRC), Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan. tarai@faculty.chiba-u.jp.
³ Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan. tarai@faculty.chiba-u.jp.
⁴ Soft Molecular Activation Research Center (SMARC), Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan.
⁵ Molecular Chirality Research Center (MCRC), Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan.
⁶ Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan.
⁷ Center for Analytical Instrumentation, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan.

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.

Publication types

Research Support, Non-U.S. Gov't