Press Releases

DATE2024.01.22 #Press Releases

Development of natural product-based macrocycles exhibiting bright circularly polarized luminescence

Efficient synthesis of chiral figure-eight-shaped macrocycles emitting strong circularly polarized luminescence through the manipulating conformation of a natural product-based scaffold

January 22, 2024

A research group at the University of Tokyo, led by Professor Hiroki Oguri from the Graduated School of Science, has developed a novel modular synthetic method for chiral D2-symmetric figure-eight-shaped macrocyclic molecules that exhibit bright circularly polarized luminescence by using a natural product-based scaffold. Previous synthetic approaches, which utilized sp2-rich aromatic compounds as building blocks for figure-eight-shaped molecules, usually required optical resolution such as chiral HPLC separation as an essential step to obtain optically pure molecules. This process presented significant bottlenecks in achieving a sufficient supply of chiral molecules in quantity.

Oguri and coworkers focused on dimeric natural products such as chimonanthine, isolated from Chimonanthus praecox. These natural products share a bispyrrolidinoindoline (BPI) scaffold, characterized by a chiral C2-symmetric dimeric structure. In this study, they successfully synthesized chiral D2-symmetric figure-eight-shaped macrocycles through a one-pot quadruple Sonogashira coupling reaction between various aromatic units and the BPI scaffold, which was prepared from amino acids. This modular synthetic platform enabled the formation of 14- to 66-membered macrocycles, allowing for flexible and precise tuning of the angle, distance, and length among intersecting chromophores. This approach, integrating natural product chemistry and materials chemistry, represents a unique and significant achievement serving as a bridge between the two independently developed fields.

Figure: Design and synthesis of chiral figure-eight-shaped macrocycles showing circularly polarized luminescence by utilizing a preorganized natural product-based scaffold.

For more details, please read the article:
Hiroki Oguri*, Tasuku Honda, Daiji Ogata, Makoto Tsurui, Satoshi Yoshida, Sota Sato, Takahiro Muraoka, Yuichi Kitagawa, Yasuchika Hasegawa*, Junpei Yuasa*, Hiroki Oguri* (* responsible author)
 2024. Rapid Synthesis of Chiral Figure-Eight Macrocycles Using a Preorganized Natural Product-Based Scaffold. Angewandte Chemie International Edition. DOI: 10.1002/anie.202318548.