Development of Asymmetric Reactions Based on Donor·Acceptor Bifunctional Catalyst Concept

2020 Fiscal Year Final Research Report

• Project/Area Number: 16H02274
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Nagoya University
• Principal Investigator: Kitamura Masato 名古屋大学, 創薬科学研究科, 教授 (50169885)
• Project Period (FY): 2016-04-01 – 2021-03-31
• Keywords: 不斉触媒反応 / 二官能性触媒 / 反応機構解明

Outline of Final Research Achievements

Recently, we have developed a new dehydrative allylation/deallylation catalyst, quinaldic acid (QAH)-CpRu, which improves the usefulness of allylic protecting groups. From this catalysis as a starting point, we have developed a soft Lewis acid/hard Bronsted acid-combined catalyst consisting of a new optically active picolinic acid-type ligand as well as a CpRu complex with a new chiral sp2 nitrogen-based bidentate ligand, combined with a Bronsted acid. These catalysts enabled new Tsuji-Trost (T-T)-type reaction with dehydrative manner. In this work, these two catalytic systems were thoroughly extended to substrate applicability and mechanistic studies were carried out for the estimation of reaction pathways and the origin of the reactive enantioselectivity.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

Tsuji-Trost型反応は、様々な有用生理活性物質の合成を可能とし，まさに有機合成の確たる基盤の一角をなしている。我々が開発した二つの触媒系は、アリルアルコールを直接に用いて、様々なプロトン性求核剤を脱水的にアリル化できる初めての例である。共生成物は「水」だけなので、生成物単離の操作性も高く、持続性社会の実現の一角をなすと期待される。弱酸性条件を用いる反応の特性は，従来法では不可能であった様々な反応形態を実現する可能性を秘める。本手法の有用性をさらに高める本研究課題の社会的意義は極めて高い。