Assembly catalysts for adaptive reaction control

2021 Fiscal Year Final Research Report

• Project/Area Number: 19K05483
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Tokyo University of Science
• Principal Investigator: Imahori Tatsushi 東京理科大学, 工学部工業化学科, 准教授 (90433515)
• Project Period (FY): 2019-04-01 – 2022-03-31
• Keywords: 適応型化学反応制御 / 集積型触媒

Outline of Final Research Achievements

In this study, we have developed supramolecular catalysts using weak pai-interactions to accomplish adaptive reaction control, in which catalyst changes the reaction space according to substrate and/or reactant to construct suitable reaction space and efficiently promote reaction. Adaptive reaction control of hydrolytic epoxide-opening reaction of meso-epoxides by self-assembly Co(III)-salen catalyst demonstrated efficient and highly stereoselective reactions with wide scope. Adaptive reaction control of 1,4-cyanation of alfa,beta-unsaturated imides by self-assembly Al(III)-salen catalyst demonstrated efficient and highly stereoselective reactions with wide scope, too. A novel hetero-assembly catalyst system with Co(III)-salen catalyst and Al(III)-salen catalyst using pai-donor-acceptor interactions was developed, and specific acceleration of epoxide-opening with trimethylsilyl cyanide has been found by using the hertero-assembly catalyst system.

Free Research Field

有機化学

Academic Significance and Societal Importance of the Research Achievements

従来の触媒は、高度に設計された反応空間が共有結合と配位結合や水素結合等の比較的強い非共有結合性相互作用によって強固に組み上げられており、触媒反応空間に入り込めない反応基質・反応剤は効率的に触媒反応が進行しない。つまり、高効率高選択的な化学反応を進行させる分子触媒は多数開発されているものの、反応基質・反応剤に対する広い適用性と高い効率性・選択性を兼ね備えた分子触媒の開発は困難であった。本研究で開発した集積性の触媒は、柔軟な反応空間を有し、反応気質や反応剤に合わせて適切な反応空間をとり、効率的な反応を広く進行させることができる。新しい適合型の化学反応制御によって、新たな反応を実現することができる。