Unusually Short H⋅⋅⋅H Contacts in Intramolecularly Cyclized Helically Fused Anthracenes
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- Hiroki Fukuda
- Department of Chemistry, School of Science Tokyo Institute of Technology 2-12-1 Ookayama, Meguro-ku Tokyo 152-8551 Japan
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- Eiji Tsurumaki
- Department of Chemistry, School of Science Tokyo Institute of Technology 2-12-1 Ookayama, Meguro-ku Tokyo 152-8551 Japan
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- Kan Wakamatsu
- Department of Chemistry, Faculty of Science Okayama University of Science 1-1 Ridaicho, Kita-ku Okayama 700-0005 Japan
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- Shinji Toyota
- Department of Chemistry, School of Science Tokyo Institute of Technology 2-12-1 Ookayama, Meguro-ku Tokyo 152-8551 Japan
書誌事項
- 公開日
- 2024-06-26
- 資源種別
- journal article
- 権利情報
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- http://creativecommons.org/licenses/by/4.0/
- DOI
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- 10.1002/chem.202401627
- 公開者
- Wiley
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説明
<jats:title>Abstract</jats:title><jats:p>The intramolecular coupling of dichloro‐substituted helically fused anthracenes using the Yamamoto coupling yielded cyclized products with sterically congested molecular structures. The X‐ray analysis and DFT calculations showed that the aromatic framework adopted a nonplanar structure with a twisted conformation about the newly formed single bond, which acts as a chiral axis. Interestingly, the X‐ray structure obtained through the Hirshfeld atom refinement revealed short interatomic distances between the inner hydrogen atoms (1.648–1.692 Å), much shorter than the sum of their van der Waals radii. Owing to these unusually short contacts, the <jats:sup>1</jats:sup>H NMR spectrum exhibited a significant deshielding (12.5 ppm) and a large nuclear Overhauser effect (44 %). Additionally, the IR spectrum displayed a high‐frequency shift of the C−H stretching vibration. These observations, along with the noncovalent interaction plot indicative of a characteristic steric environment, strongly support the presence of steric hindrance. Moreover, dynamic NMR measurement of the mesityl‐substituted derivative yielded a barrier to helical inversion of 84 kJ mol<jats:sup>−1</jats:sup>. The optical properties and crystal packing of the cyclized products are also reported.</jats:p>
収録刊行物
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- Chemistry – A European Journal
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Chemistry – A European Journal 30 (41), 2024-06-26
Wiley
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詳細情報 詳細情報について
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- CRID
- 1360021391868254336
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- ISSN
- 15213765
- 09476539
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- 資料種別
- journal article
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- データソース種別
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- Crossref
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