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Strain-Induced Ring Expansion Reactions of Calix[3]pyrrole-Related Macrocycles
| Title: | Strain-Induced Ring Expansion Reactions of Calix[3]pyrrole-Related Macrocycles |
| Authors: | Inaba, Yuya Browse this author | | Kakibayashi, Yu Browse this author | | Ide, Yuki Browse this author | | Pirillo, Jenny Browse this author | | Hijikata, Yuh Browse this author | | Yoneda, Tomoki Browse this author | | Inokuma, Yasuhide Browse this author →KAKEN DB |
| Keywords: | calixarenes | | macrocycles | | porphyrinoids | | reaction mechanisms | | strained molecules |
| Issue Date: | 22-Mar-2022 |
| Publisher: | Wiley-Blackwell |
| Journal Title: | Chemistry-A European journal |
| Volume: | 28 |
| Issue: | 17 |
| Start Page: | e202200056 |
| Publisher DOI: | 10.1002/chem.202200056 |
| Abstract: | The recent discovery of calix[3]pyrrole, a porphyrinogen-like tripyrrolic macrocycle, has provided an unprecedented strain-induced ring expansion reaction into calix[6]pyrrole. Here, we synthesized calix[n]furan[3-n]pyrrole (n=1 similar to 3) macrocycles to investigate the reaction scope and mechanism of the ring expansion. Single crystal X-ray analysis and theoretical calculations revealed that macrocyclic ring strain increases as the number of inner NH sites increases. While calix[1]furan[2]pyrrole exhibited almost quantitative conversion into calix[2]furan[4]pyrrole within 5 minutes, less-strained calix[2]furan[1]pyrrole and calix[3]furan were inert. However, N-methylation of calix[2]furan[1]pyrrole induced a ring-expansion reaction that enabled the isolation of a linear reaction intermediate. The mechanism analysis revealed that the ring expansion consists of regioselective ring cleavage and subsequent cyclodimerization. This reaction was further utilized for synthesis of calix[6]-type macrocycles. |
| Rights: | This is the peer reviewed version of the following article: Y. Inaba, Y. Kakibayashi, Y. Ide, J. Pirillo, Y. Hijikata, T. Yoneda, Y. Inokuma, Chem. Eur. J. 2022, 28, e202200056, which has been published in final form at https://doi.org/10.1002/chem.202200056. 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) |
| URI: | http://hdl.handle.net/2115/87974 |
| 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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