{"@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/1361975842845752832.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1021/acs.organomet.8b00684"}},{"identifier":{"@type":"URI","@value":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.8b00684"}}],"resourceType":"学術雑誌論文(journal article)","dc:title":[{"@value":"Computational Mechanistic Study on the Nickel-Catalyzed C–H/N–H Oxidative Annulation of Aromatic Amides with Alkynes: The Role of the Nickel (0) Ate Complex"}],"description":[{"notation":[{"@value":"Density functional theory (DFT) was used to unveil intimate mechanistic insights on the monodentate-chelation system that is used in the Ni-catalyzed C–H/N–H oxidative annulation of aromatic amides with alkynes, a reaction that was originally reported by our group  Chem Sci. 2017, 8, 6650−6655, DOI: 10.1039/C7SC01750B). The proposed reaction mechanism involves two reaction paths. The initial path is initiated by Ni(II), and the other, the main catalytic cycle, is initiated by Ni(0). Both paths require the presence of a catalytic amount of KOBut. The results of the DFT studies presented here indicate that the rate-determining step in the initial Ni(II) system involves a concerted metalation–deprotonation (CMD) mechanism and an anionic Ni(0) ate complex is the key intermediate in the main catalytic cycle. Furthermore, a previously proposed oxidative addition–alkyne insertion sequence is revised to a ligand-to-ligand hydrogen transfer (LLHT) mechanism, which is the rate-determining step in the main catalytic..."}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1381975842845752835","@type":"Researcher","foaf:name":[{"@value":"Ken Yamazaki"}],"jpcoar:affiliationName":[{"@value":"Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan"}]},{"@id":"https://cir.nii.ac.jp/crid/1381975842845752836","@type":"Researcher","foaf:name":[{"@value":"Atsushi Obata"}],"jpcoar:affiliationName":[{"@value":"Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan"}]},{"@id":"https://cir.nii.ac.jp/crid/1381975842845752833","@type":"Researcher","foaf:name":[{"@value":"Akane Sasagawa"}],"jpcoar:affiliationName":[{"@value":"Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 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