{"@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/1360011144862990464.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1002/adsc.201600629"}},{"identifier":{"@type":"URI","@value":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fadsc.201600629"}},{"identifier":{"@type":"URI","@value":"https://advanced.onlinelibrary.wiley.com/doi/pdf/10.1002/adsc.201600629"}}],"dc:title":[{"@value":"Radical Stability as a Guideline in C–H Amination Reactions"}],"description":[{"type":"abstract","notation":[{"@value":"<jats:title>Abstract</jats:title><jats:p>The stability of N‐centered radicals and radical cations of potential relevance in C–H amidation reactions has been quantified using highly accurate theoretical methods. Combination with available C–H bond energies for substrate fragments allows for the prediction of reaction enthalpies in 1,5‐hydrogen atom transfer (HAT) steps frequently encountered in reactions such as the Hofmann–Löffler–Freytag (HLF) reaction. Protonation of N‐radicals is found to be essential in classical HLF reactions for thermochemically feasible HAT steps. The stability of neutral N‐radicals depends strongly on the type of <jats:italic>N</jats:italic>‐substituent. Among the electron‐withdrawing substituents, the trifluoroacetyl (TFA) group is the least and the toluenesulfonyl (tosyl) group the most stabilizing. This implies that TFA‐aminyl radicals have the broadest and tosyl‐aminyl radicals the smallest window of synthetic applicability. In how far the intramolecular C–H amidation reactions compete with hydrogen abstraction from common organic solvents can be judged based on a comparison of reaction thermodynamics.</jats:p><jats:p><jats:boxed-text content-type=\"graphic\" position=\"anchor\"><jats:graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" mimetype=\"image/png\" position=\"anchor\" specific-use=\"enlarged-web-image\" xlink:href=\"graphic/adsc201600629-toc-0001-m.png\"><jats:alt-text>magnified image</jats:alt-text></jats:graphic></jats:boxed-text>\n</jats:p>"}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1380011144862990464","@type":"Researcher","foaf:name":[{"@value":"Davor Šakić"}],"jpcoar:affiliationName":[{"@value":"University of Zagreb Faculty of Pharmacy and Biochemistry  Ante Kovačića 1 10000 Zagreb Croatia"}]},{"@id":"https://cir.nii.ac.jp/crid/1380011144862990465","@type":"Researcher","foaf:name":[{"@value":"Hendrik Zipse"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry LMU Muenchen  Butenandtstrasse 5–13 81377 Muenchen Germany"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"16154150"},{"@type":"EISSN","@value":"16154169"}],"prism:publicationName":[{"@value":"Advanced Synthesis & Catalysis"}],"dc:publisher":[{"@value":"Wiley"}],"prism:publicationDate":"2016-09-21","prism:volume":"358","prism:number":"24","prism:startingPage":"3983","prism:endingPage":"3991"},"reviewed":"false","dc:rights":["http://onlinelibrary.wiley.com/termsAndConditions#vor"],"url":[{"@id":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fadsc.201600629"},{"@id":"https://advanced.onlinelibrary.wiley.com/doi/pdf/10.1002/adsc.201600629"}],"createdAt":"2016-09-21","modifiedAt":"2025-10-06","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1360004233142278400","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Intramolecular, Site-Selective, Iodine-Mediated, Amination of Unactivated (<i>sp</i><sup>3</sup>)C–H Bonds for the Synthesis of Indoline Derivatives"}]},{"@id":"https://cir.nii.ac.jp/crid/1360567179880006272","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Photoredox‐Catalyzed Site‐Selective α‐C(sp<sup>3</sup>)−H Alkylation of Primary Amine Derivatives"}]},{"@id":"https://cir.nii.ac.jp/crid/1360572092664824832","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Mannich-type allylic C–H functionalization of enol silyl ethers under photoredox–thiol hybrid catalysis"}]},{"@id":"https://cir.nii.ac.jp/crid/1360848658544933248","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Sulfonamides as new hydrogen atom transfer (HAT) catalysts for photoredox allylic and benzylic C–H arylations"}]},{"@id":"https://cir.nii.ac.jp/crid/1360849942948655104","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Zwitterionic 1,2,3-Triazolium Amidate as a Catalyst for Photoinduced Hydrogen-Atom Transfer Radical Alkylation"}]},{"@id":"https://cir.nii.ac.jp/crid/1360865815492107648","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Zwitterionic Acridinium Amidate: A Nitrogen-Centered Radical Catalyst for Photoinduced Direct Hydrogen Atom Transfer"}]},{"@id":"https://cir.nii.ac.jp/crid/1361412893390105344","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Transition-metal-free Intramolecular C–H amination of sulfamate esters and<i>N</i>-alkylsulfamides"}]}],"dataSourceIdentifier":[{"@type":"CROSSREF","@value":"10.1002/adsc.201600629"},{"@type":"CROSSREF","@value":"10.1021/acscatal.9b04491_references_DOI_E6L8NCL6DfjqUwmDmerGOEGtULk"},{"@type":"CROSSREF","@value":"10.1021/acs.orglett.7b00846_references_DOI_E6L8NCL6DfjqUwmDmerGOEGtULk"},{"@type":"CROSSREF","@value":"10.1002/anie.201812227_references_DOI_E6L8NCL6DfjqUwmDmerGOEGtULk"},{"@type":"CROSSREF","@value":"10.1039/d0ob01862g_references_DOI_E6L8NCL6DfjqUwmDmerGOEGtULk"},{"@type":"CROSSREF","@value":"10.1039/c7cc09457d_references_DOI_E6L8NCL6DfjqUwmDmerGOEGtULk"},{"@type":"CROSSREF","@value":"10.1002/anie.202404890_references_DOI_E6L8NCL6DfjqUwmDmerGOEGtULk"},{"@type":"CROSSREF","@value":"10.1039/c9cc06410a_references_DOI_E6L8NCL6DfjqUwmDmerGOEGtULk"}]}