Development of Novel Chiral Dinuclear Complexes for Catalytic Asymmetric C-H Bond Functionalization

2020 Fiscal Year Final Research Report

• Project/Area Number: 17H03049
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: Matsunaga Shigeki 北海道大学, 薬学研究院, 教授 (50334339)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Keywords: 不斉触媒 / 不斉合成 / C-H活性化 / パラジウム / シッフ塩基

Outline of Final Research Achievements

In this research, we tried to develop a new catalyst for enantio-induction. The generation of active metal species for C-H activation under unique chiral environment was the key. To achieve original and novel chiral system, dinucleating Schiff base system was designed. After intensive optimization of the catalyst structure and catalysts modules, we found that the chiral dinuclear Schiff base catalyst consisted of chiral binaphthyl diamine, chiral sulfoxide unit, palladium and copper was the best, showing high catalytic activity as well as enantioselctivity in intramolecular allylic C-H amination reactions. Broad substrate scope was also confirmed using the Pd-Cu Schiff base catalyst.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

有機化合物に普遍的に存在する炭素ー水素結合のうち、特定の部分を化学選択的に活性化し、化学変換するプロセスは廃棄物の少ない環境調和性の高い合成手法の開発に繋がる。特に、医薬品に見られる含窒素化合物の立体選択的な合成法は得られる生成物の付加価値が高く、その効率的かつ環境調和性の高い合成法の開発が強く求められている。本研究では、炭素ー水素結合を選択的に活性化し、窒素基を導入する新しいキラル触媒の創出に取り組み、従来法では得られない生成物を得る手法を確立した。