{"@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/1361981469932486912.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1002/hlca.19980810513"}},{"identifier":{"@type":"URI","@value":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fhlca.19980810513"}},{"identifier":{"@type":"URI","@value":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/hlca.19980810513"}}],"dc:title":[{"@value":"β<sup>2</sup>‐ and β<sup>3</sup>‐Peptides with Proteinaceous Side Chains: Synthesis and solution structures of constitutional isomers, a novel helical secondary structure and the influence of solvation and hydrophobic interactions on folding"}],"description":[{"type":"abstract","notation":[{"@value":"<jats:title>Abstract</jats:title><jats:p>Enantiomerically pure β‐amino‐acid derivatives with the side chains of Ala, Val, and Leu in the 2‐ or 3‐position (β<jats:sup>2</jats:sup>‐ and β<jats:sup>3</jats:sup>‐amino acids, resp.), as well as with substituents in both the 2‐ and 3‐positions (β<jats:sup>2,3</jats:sup>‐amino acids, of <jats:italic>like</jats:italic>‐configuration) have been prepared (compounds <jats:bold>8</jats:bold>–<jats:bold>17</jats:bold>) and incorporated (by stepwise synthesis and fragment coupling, intermediates <jats:bold>24</jats:bold>–<jats:bold>34</jats:bold>) into β‐hexa‐, β‐hepta‐, and β‐dodecapeptides (<jats:bold>1</jats:bold>–<jats:bold>17</jats:bold>). The new and some of the previously prepared β‐peptides (<jats:bold>35</jats:bold>–<jats:bold>39</jats:bold>) showed NH/ND exchange rates (in MeOH at room temperature) with τ<jats:sub>1/2</jats:sub> values of up to 60 days, unrivalled by short chain α‐peptides. All β‐peptides <jats:bold>1</jats:bold>–<jats:bold>7</jats:bold> were designed to be able to attain the previously described <jats:italic>3</jats:italic><jats:sub>1</jats:sub>‐helical structure (<jats:italic>Figs. 1</jats:italic> and <jats:italic>2</jats:italic>). CD Measurements (<jats:italic>Fig. 4</jats:italic>), indicating a new secondary structure of certain β‐peptides constructed of β<jats:sup>2</jats:sup>‐ and β<jats:sup>3</jats:sup>‐amino acids, were confirmed by detailed NMR solution‐structure analyses: a β<jats:sup>2</jats:sup>‐heptapeptide (<jats:bold>2c</jats:bold>) and a β<jats:sup>2,3</jats:sup>‐hexapeptide (<jats:bold>7c</jats:bold>) have the <jats:italic>3</jats:italic><jats:sub>1</jats:sub>‐helical structure (<jats:italic>Figs. 6</jats:italic> and <jats:italic>7</jats:italic>), while to a β<jats:sup>2</jats:sup>/β<jats:sup>3</jats:sup>‐hexapeptide (<jats:bold>4</jats:bold>) with alternating substitution pattern H‐(β<jats:sup>2</jats:sup>‐Xaa‐β<jats:sup>3</jats:sup>‐Xaa)<jats:sub>3</jats:sub>‐OH a novel, unusual helical structure (in (D<jats:sub>5</jats:sub>)pyridine, <jats:italic>Fig. 8</jats:italic>; and in CD<jats:sub>3</jats:sub>OH, <jats:italic>Figs. 9</jats:italic> and <jats:italic>10</jats:italic>) was assigned, with a central ten‐membered and two terminal twelve‐membered H‐bonded rings, and with CO and NH bonds pointing alternatively up and down along the axis of the helix (<jats:italic>Fig. 11</jats:italic>). Thus, for the first time, two types of β‐peptide turns have been identified in solution. Hydrophobic interactions <jats:italic>of</jats:italic> and hindrance to solvent accessibility <jats:italic>by</jats:italic> the aliphatic side chains are discussed as possible factors influencing the relative stability of the two types of helices.</jats:p>"}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1381981469932486917","@type":"Researcher","foaf:name":[{"@value":"Dieter Seebach"}]},{"@id":"https://cir.nii.ac.jp/crid/1381981469932487041","@type":"Researcher","foaf:name":[{"@value":"Stefan Abele"}]},{"@id":"https://cir.nii.ac.jp/crid/1381981469932487043","@type":"Researcher","foaf:name":[{"@value":"Karl Gademann"}]},{"@id":"https://cir.nii.ac.jp/crid/1381981469932487040","@type":"Researcher","foaf:name":[{"@value":"Gilles Guichard"}]},{"@id":"https://cir.nii.ac.jp/crid/1381981469932486918","@type":"Researcher","foaf:name":[{"@value":"Tobias Hintermann"}]},{"@id":"https://cir.nii.ac.jp/crid/1381981469932486914","@type":"Researcher","foaf:name":[{"@value":"Bernhard Jaun"}]},{"@id":"https://cir.nii.ac.jp/crid/1381981469932487042","@type":"Researcher","foaf:name":[{"@value":"Jennifer L. Matthews"}]},{"@id":"https://cir.nii.ac.jp/crid/1380579818624399744","@type":"Researcher","foaf:name":[{"@value":"Jürg V. Schreiber"}]},{"@id":"https://cir.nii.ac.jp/crid/1381981469932486915","@type":"Researcher","foaf:name":[{"@value":"Lukas Oberer"}]},{"@id":"https://cir.nii.ac.jp/crid/1381981469932486912","@type":"Researcher","foaf:name":[{"@value":"Ulrich Hommel"}]},{"@id":"https://cir.nii.ac.jp/crid/1381981469932486916","@type":"Researcher","foaf:name":[{"@value":"Hans Widmer"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"0018019X"},{"@type":"EISSN","@value":"15222675"}],"prism:publicationName":[{"@value":"Helvetica Chimica Acta"}],"dc:publisher":[{"@value":"Wiley"}],"prism:publicationDate":"1998-01","prism:volume":"81","prism:number":"5-8","prism:startingPage":"932","prism:endingPage":"982"},"reviewed":"false","dc:rights":["http://onlinelibrary.wiley.com/termsAndConditions#vor"],"url":[{"@id":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fhlca.19980810513"},{"@id":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/hlca.19980810513"}],"createdAt":"2004-12-28","modifiedAt":"2023-08-31","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1360846644034820096","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Asymmetric Synthesis of <i>β</i>-Amino Acids by Addition of Chiral Enolates to Nitrones via <i>N</i>-Acyloxyiminium Ions"}]},{"@id":"https://cir.nii.ac.jp/crid/1390001204121695360","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Direct Synthesis of N-Hydroxy .BETA.-Amino Acid Esters from Carboxylic Esters and Nitrones."},{"@value":"Direct Synthesis of <i>N</i>-Hydroxy <i>β</i>-Amino Acid Esters from Carboxylic Esters and Nitrones"}]},{"@id":"https://cir.nii.ac.jp/crid/2050588892094607616","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Synthesis and structural analysis of ruthenium-bound norvaline peptides"}]}],"dataSourceIdentifier":[{"@type":"CROSSREF","@value":"10.1002/hlca.19980810513"},{"@type":"CROSSREF","@value":"10.1246/bcsj.73.2423_references_DOI_aQHQT2e5FFLNl2NiHpX7qRW84Si"},{"@type":"CROSSREF","@value":"10.1246/bcsj.73.2805_references_DOI_aQHQT2e5FFLNl2NiHpX7qRW84Si"},{"@type":"CROSSREF","@value":"10.1246/cl.170012_references_DOI_aQHQT2e5FFLNl2NiHpX7qRW84Si"}]}