Precise Design and Functionalization of Asymmetric Supramolecular Spaces: Predictable Asymmetric Reactions based on Molecular Adsorption

2018 Fiscal Year Final Research Report

• Project/Area Number: 16K13959
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Inorganic chemistry
• Research Institution: The University of Tokyo
• Principal Investigator: Shionoya Mitsuhiko 東京大学, 大学院理学系研究科(理学部), 教授 (60187333)
• Project Period (FY): 2016-04-01 – 2019-03-31
• Keywords: 不斉超空間 / エナンチオ選択的反応 / 多孔性超分子結晶 / 不斉分子認識 / 超分子金属錯体 / 触媒反応

Outline of Final Research Achievements

This study aimed to establish synthetic methods of porous chiral crystals by utilizing self-assembly of helical macrocyclic trinuclear Pd(II) complexes, and to develop reaction spaces for asymmetric reactions which possibly allow highly specific adsorption of substrates and site- and face-selective molecular adsorption. Firstly, we have succeeded in face-selective adsorption of prochiral molecules by utilizing the ability of asymmetric reagents to bind selectively to only one site of enantiomerically-paired binding pockets. In this connection, it was also found that photo-induced olefin migration reactions take place in this nano-channel. Moreover, self-assembly of the same Pd(II) complexes was found to produce homochiral porous crystals in the presence of sugar derivatives. Asymmetric Diels Alder reactions took place, though the enantiomeric excess was rather low, in the nano-pocket space in this crystal.

Free Research Field

超分子化学　生物無機化学

Academic Significance and Societal Importance of the Research Achievements

中空構造を持つ多孔性配位高分子、ゼオライト、分子カプセル、ミセル・ベシクル等は、分子の吸着、変換、輸送の場を提供する優れた物質群である。本研究で開拓された多孔性結晶は、分子認識能を有する大環状金属錯体の自己集積化を利用して簡便に合成が可能であり、分子認識・捕捉能と触媒機能を兼ね備えた不斉反応場の開発に新しい学術的意義を与えるものである。本研究成果は、近接効果と配向効果に基づくエネルギー低減型の高選択的不斉反応につながるものであり、社会的意義も高い。