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Calix[3]pyrrole : A Missing Link in Porphyrin-Related Chemistry
| 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 | | Pyrroles | | Molecular structure | | Macrocycles |
| 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 https://pubs.acs.org/articlesonrequest/AOR-2PPNXJANHHH97EDJRIDY. |
| Type: | article (author version) |
| URI: | http://hdl.handle.net/2115/86376 |
| 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)
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Submitter: 猪熊 泰英
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