{"@context":{"@vocab":"https://cir.nii.ac.jp/schema/1.0/","rdfs":"http://www.w3.org/2000/01/rdf-schema#","dc":"http://purl.org/dc/elements/1.1/","dcterms":"http://purl.org/dc/terms/","foaf":"http://xmlns.com/foaf/0.1/","prism":"http://prismstandard.org/namespaces/basic/2.0/","cinii":"http://ci.nii.ac.jp/ns/1.0/","datacite":"https://schema.datacite.org/meta/kernel-4/","ndl":"http://ndl.go.jp/dcndl/terms/","jpcoar":"https://github.com/JPCOAR/schema/blob/master/2.0/"},"@id":"https://cir.nii.ac.jp/crid/1361699993944503680.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1002/hlca.200900376"}},{"identifier":{"@type":"URI","@value":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fhlca.200900376"}},{"identifier":{"@type":"URI","@value":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/hlca.200900376"}}],"dc:title":[{"@value":"Experimental and Theoretical Conformational Analysis of 5‐Benzylimidazolidin‐4‐one Derivatives – a ‘Playground’ for Studying Dispersion Interactions and a ‘Windshield‐Wiper’ Effect in Organocatalysis"}],"description":[{"type":"abstract","notation":[{"@value":"AbstractThe PF6 salts of 5‐benzyl‐1‐isopropylidene‐ and 5‐benzyl‐1‐cinnamylidene‐3‐methylimidazolidin‐4‐ones 1 (Scheme) with various substituents in the 2‐position have been prepared, and single crystals suitable for X‐ray structure determination have been obtained of 14 such compounds, i.e., 2–10 and 12–16 (Figs. 2–5). In nine of the structures, the Ph ring of the benzyl group resides above the heterocycle, in contact with the cis‐substituent at C(2) (staggered conformation A; Figs. 1–3); in three structures, the Ph ring lies above the iminium π‐plane (staggered conformation B; Figs. 1 and 4); in two structures, the benzylic CC bond has an eclipsing conformation (C; Figs. 1 and 5) which places the Ph ring simultaneously at a maximum distance with its neighbors, the CO group, the NC‐π‐system, and the cis‐substituent at C(2) of the heterocycle. It is suggested by a qualitative conformational analysis (Fig. 6) that the three staggered conformations of the benzylic CC bond are all subject to unfavorable steric interactions, so that the eclipsing conformation may be a kind of ‘escape’. State‐of‐the‐art quantum‐chemical methods, with large AO basic sets (near the limit) for the single‐point calculations, were used to compute the structures of seven of the 14 iminium ions, i.e., 3, 4/12, 5–7, 13, and 16 (Table) in the two staggered conformations, A and B, with the benzylic Ph group above the ring and above the iminium π‐system, respectively. In all cases, the more stable computed conformer (‘isolated‐molecule’ structure) corresponds to the one present in the crystal (overlay in Fig. 7). The energy differences are small (≤2 kcal/mol) which, together with the result of a potential‐curve calculation for the rotation around the benzylic CC bond of one of the structures, 16 (Fig. 8), suggests that the benzyl group is more or less freely rotating at ambident temperatures. The importance of intramolecular London dispersion (benzene ring in ‘contact’ with the cis‐substituent in conformation A) for DFT and other quantum‐chemical computations is demonstrated; the benzyl‐imidazolidinones 1 appear to be ideal systems for detecting dispersion contributions between a benzene ring and alkyl or aryl CH groups. Enylidene ions of the type studied herein are the reactive intermediates of enantioselective organocatalytic conjugate additions, Diels–Alder reactions, and many other transformations involving α,β‐unsaturated carbonyl compounds. Our experimental and theoretical results are discussed in view of the performance of 5‐benzyl‐imidazolidinones as enantioselective catalysts."}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1381699993944503682","@type":"Researcher","foaf:name":[{"@value":"Dieter Seebach"}]},{"@id":"https://cir.nii.ac.jp/crid/1380579925473409280","@type":"Researcher","foaf:name":[{"@value":"Uroš Grošelj"}]},{"@id":"https://cir.nii.ac.jp/crid/1381699993944503683","@type":"Researcher","foaf:name":[{"@value":"W. Bernd Schweizer"}]},{"@id":"https://cir.nii.ac.jp/crid/1381699993944503681","@type":"Researcher","foaf:name":[{"@value":"Stefan Grimme"}]},{"@id":"https://cir.nii.ac.jp/crid/1380579925473409281","@type":"Researcher","foaf:name":[{"@value":"Christian Mück‐Lichtenfeld"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"0018019X"},{"@type":"EISSN","@value":"15222675"}],"prism:publicationName":[{"@value":"Helvetica Chimica Acta"}],"dc:publisher":[{"@value":"Wiley"}],"prism:publicationDate":"2010-01","prism:volume":"93","prism:number":"1","prism:startingPage":"1","prism:endingPage":"16"},"reviewed":"false","dc:rights":["http://onlinelibrary.wiley.com/termsAndConditions#vor"],"url":[{"@id":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fhlca.200900376"},{"@id":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/hlca.200900376"}],"createdAt":"2010-01-20","modifiedAt":"2023-11-21","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1360004230130933376","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Organocatalyzed Michael Addition of Aldehydes to Nitro Alkenes – Generally Accepted Mechanism Revisited and Revised"}]},{"@id":"https://cir.nii.ac.jp/crid/1360285708566235264","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Enhancement of stereoselectivities in asymmetric synthesis using fluorinated solvents, auxiliaries, and catalysts"}]}],"dataSourceIdentifier":[{"@type":"CROSSREF","@value":"10.1002/hlca.200900376"},{"@type":"CROSSREF","@value":"10.1002/hlca.201100122_references_DOI_IT5SQf9A8532tgTD6nYP2fTAYIa"},{"@type":"CROSSREF","@value":"10.1039/c4ra11860j_references_DOI_IT5SQf9A8532tgTD6nYP2fTAYIa"}]}