Dynamic Stereocontrolled Synthesis of Atropisomers via Highly Organized Hydrogen Bond Network

2015 Fiscal Year Final Research Report

• Project/Area Number: 25810025
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Tokyo University of Agriculture and Technology (2015); Gakushuin University (2013-2014)
• Principal Investigator: Mori Keiji 東京農工大学, 工学(系)研究科(研究院), 准教授 (10515076)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Keywords: 軸不斉ビアリール / 動的速度論的光学分割 / キラルリン酸触媒 / アトロプ異性体 / 還元的アミノ化

Outline of Final Research Achievements

Atropisomerism is very important chiral element, which can be seen in many useful organic molecules, such as biologically active compounds, chiral ligands, and organocatalysts. On the contrary to its usefulness, the method for asymmetric synthesis of atropisomers are scarce. Under such background, our group have been interested in the development of asymmetric synthesis of atropisomers by chiral phosphoric acid catalyzed dynamic kinetic resolution strategy. After extensive examination of the reaction conditions, we found that asymmetric reductive amination of biaryl lactols with o-hydroxyaniline were effectively catalyzed by chiral phosphoric acid with modified triarylsilyl group at 3,3’-positions to afford the desired biaryl-type benzyl amines in excellent enantioselectivities. Interestingly, the opposite enantiomer was obtained by simple changing position of the hydroxyl group in hydroxyaniline moiety from ortho- to meta-position.

Free Research Field

有機合成化学