HUSCAP logo Hokkaido Univ. logo

Hokkaido University Collection of Scholarly and Academic Papers >
Graduate School of Engineering / Faculty of Engineering >
Peer-reviewed Journal Articles, etc >

Calix[3]pyrrole : A Missing Link in Porphyrin-Related Chemistry

Files in This Item:
manuscript_revise2.pdf1.01 MBPDFView/Open
Please use this identifier to cite or link to this item:

Title: Calix[3]pyrrole : A Missing Link in Porphyrin-Related Chemistry
Authors: Inaba, Yuya Browse this author
Nomata, Yu Browse this author
Ide, Yuki Browse this author
Pirillo, Jenny Browse this author
Hijikata, Yuh Browse this author
Yoneda, Tomoki Browse this author
Osuka, Atsuhiro Browse this author
Sessler, Jonathan L. Browse this author
Inokuma, Yasuhide Browse this author →KAKEN DB
Keywords: Anions
Crystal structure
Molecular structure
Issue Date: 11-Aug-2021
Publisher: American Chemical Society
Journal Title: Journal of the American Chemical Society
Volume: 143
Issue: 31
Start Page: 12355
End Page: 12360
Publisher DOI: 10.1021/jacs.1c06331
Abstract: A long-standing question in porphyrin chemistry is why pyrrole monomers selectively form tetrapyrrolic macrocycles, whereas the corresponding tripyrrolic macrocycles are never observed. Calix[3]pyrrole, a tripyrrolic porphyrinogen-like macrocycle bearing three sp(3)-carbon linkages, is a missing link molecule that might hold the key to this enigma; however, it has remained elusive. Here we report the synthesis and strain-induced transformations of calix[3]pyrrole and its furan analogue, calix[3]furan. These macrocycles are readily accessed from cyclic oligoketones. Crystallographic and theoretical analyses reveal that these three-subunit systems possess the largest strain energy among known calix[n]-type macrocycles. The ring-strain triggers transformation of calix[3]pyrrole into first calix[6]pyrrole and then calix[4]pyrrole under porphyrin cyclization conditions. The present results help explain the absence of naturally occurring three-pyrrole macrocycles and the fact that they are not observed as products or intermediate during classic porphyrin syntheses.
Rights: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
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

Export metadata:

OAI-PMH ( junii2 , jpcoar_1.0 )

MathJax is now OFF:


 - Hokkaido University