Development of Inherently Chiral Cavitands for Catalytic Use

2021 Fiscal Year Final Research Report

• Project/Area Number: 19K05426
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
• Research Institution: Ryukoku University
• Principal Investigator: Iwasawa Tetsuo 龍谷大学, 先端理工学部, 教授 (80452655)
• Project Period (FY): 2019-04-01 – 2022-03-31
• Keywords: Inherent キラルキャビタンド / キャビタンド触媒 / 人工酵素 / Inherentキラリティー / ホスホン酸

Outline of Final Research Achievements

Synthetic development of inherent chiral cavitands those enable catalysis unthinkable heretofore has been performed, which aims to find new synthetic methodology and prominent selective transformation: thus, novel protocols that employ quinoxaline-spanned resorcin[4]arenes were established and new chiral molecules unachievable so far were synthesized. When the inherent chiral platform was attempted in epoxidation of tethered allyl groups, the chirality was successfully transferred into the inside allyl substructure. In addition, the inherent chiral phosphoric acid was prepared for making complex with a guest molecule of (2-vinyl)pyridine, and competitive conjugate addition reactions between two nucleophiles were demonstrated: In contrast to control acid reagents, the cavitand typed-acid made the product distribution totally reversed. This new finding indicates the supramolecular space can regulate the chemical selectivity, and will lead us to achieve potent chemical transformations.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

不斉触媒の研究は過去数十年に渡り行われてきたが、グリーンケミストリーの観点からは未だ成熟していない。そのため、革新的な解決を可能にする新しい概念に依拠した触媒開発が求められてきた。本研究では、アキラルな置換基を時計回りと反時計回りに配置することによって生じるキラリティーのみを不斉源としたキャビタンド触媒の創出に成功し、従来にはない触媒反応場の構築を達成した。この成果の社会性との関わりにおける意義は、環境にやさしい物質合成との関連において、新しい製法・製造原理を生み出す価値を持つ。また、学術との関連において、新しい不斉反応場の概念をベースにしたキラル化学の進展を促す価値を持つ。