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Chiral Calix[3]pyrrole Derivatives: Synthesis, Racemization Kinetics, and Ring Expansion to Calix[9]- and Calix[12]pyrrole Analogues

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Title: Chiral Calix[3]pyrrole Derivatives: Synthesis, Racemization Kinetics, and Ring Expansion to Calix[9]- and Calix[12]pyrrole Analogues
Authors: Inaba, Yuya Browse this author
Yang, Jian Browse this author
Kakibayashi, Yu Browse this author
Yoneda, Tomoki Browse this author →KAKEN DB
Ide, Yuki Browse this author →KAKEN DB
Hijikata, Yuh Browse this author →KAKEN DB
Pirillo, Jenny Browse this author
Saha, Ranajit Browse this author
Sessler, Jonathan L. Browse this author
Inokuma, Yasuhide Browse this author →KAKEN DB
Keywords: Calixarenes
Racemization Kinetics
Ring Expansion
Issue Date: 3-Apr-2023
Publisher: Wiley-Blackwell
Journal Title: Angewandte chemie - international edition
Volume: 62
Issue: 15
Start Page: e202301460
Publisher DOI: 10.1002/anie.202301460
PMID: 36785520
Abstract: Chiral pyrrolic macrocycles continue to attract interest. However, their molecular design remains challenging. Here, we report a calixpyrrole-based chiral macrocyclic system, calix[1]furan[1]pyrrole[1]thiophene (1), synthesized from an oligoketone. Macrocycle 1 adopts a partial cone conformation in the solid state, and undergoes racemization via ring inversion. Molecular dynamics simulations revealed that inversion of the thiophene is the rate determining step. Pyrrole N-methylation suppressed racemization and permitted chiral resolution. Enantioselective N-methylation also occurred in the presence of a chiral ammonium salt, although the stereoselectivity is modest. A unique feature of 1 is that it acts as a useful synthetic precursor to yield several calix[n]furan[n]pyrrole[n]thiophene products (n=2-4), including a calix[12]pyrrole analogue that to our knowledge constitutes the largest calix[n]pyrrole-like species to be structurally characterized.
Rights: This is the peer reviewed version of the following article: Inaba, Y., Yang, J., Kakibayashi, Y., Yoneda, T., Ide, Y., Hijikata, Y., Pirillo, J., Saha, R., Sessler, J. L., Inokuma, Y., /Angew. Chem. Int. Ed./ 2023, 62, e202301460, which has been published in final form at This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
Type: article (author version)
Appears in Collections:工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 猪熊 泰英

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