Rapid Synthesis of Chiral Figure‐Eight Macrocycles Using a Preorganized Natural Product‐Based Scaffold

Chiral D2‐symmetric figure‐eight shaped macrocycles are promising scaffolds for amplifying the chiroptical properties of π‐conjugated systems. By harnessing the inherent and adaptable conformational dynamics of a chiral C2‐symmetric bispyrrolidinoindoline (BPI) manifold, we developed an enantio‐dive...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2024-02, Vol.63 (9), p.e202318548-n/a
Main Authors: Honda, Tasuku, Ogata, Daiji, Tsurui, Makoto, Yoshida, Satoshi, Sato, Sota, Muraoka, Takahiro, Kitagawa, Yuichi, Hasegawa, Yasuchika, Yuasa, Junpei, Oguri, Hiroki
Format: Article
Language:English
Subjects:
Bispyrrolidinoindoline
Chromophores
Circular polarization
Circularly Polarized Luminescence
Couplings
Macrocycles
Natural Products
Preorganized Scaffolds
Scaffolds
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Summary:Chiral D2‐symmetric figure‐eight shaped macrocycles are promising scaffolds for amplifying the chiroptical properties of π‐conjugated systems. By harnessing the inherent and adaptable conformational dynamics of a chiral C2‐symmetric bispyrrolidinoindoline (BPI) manifold, we developed an enantio‐divergent modular synthetic platform to rapidly generate a diverse range of chiral macrocycles, spanning from 14‐ to 66‐membered rings, eliminating the need for optical resolution. Notably, a 32‐membered figure‐eight macrocycle showed excellent circularly polarized luminescence (CPL: |glum|=1.1×10−2) complemented by a robust emission quantum yield (Φfl=0.74), to achieve outstanding CPL brightness (BCPL: ϵ×Φfl×|glum|/2=480). Using quadruple Sonogashira couplings, this versatile synthetic platform enables precise adjustments of the angle, distance, and length among intersecting π‐conjugated chromophores. Our synthetic strategy offers a streamlined and systematic approach to significantly enhance BCPL values for a variety of chiral D2‐symmetric figure‐eight macrocycles. A chiral D2‐symmetric Figure‐eight macrocycle, which exhibits bright CPL (glum=0.011, Φfl=0.74, BCPL=480), was efficiently synthesized using a versatile C2‐symmetric natural product‐based manifold with a preorganized conformation. This rapid and modular synthetic platform allows flexible and precise tuning of the angle, distance, and length among intersecting π‐conjugated chromophores in shape‐persistent figure‐eight macrocycles.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202318548