{"@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/1363670318857017728.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1016/s0040-4020(01)91998-2"}},{"identifier":{"@type":"URI","@value":"https://api.elsevier.com/content/article/PII:S0040402001919982?httpAccept=text/xml"}},{"identifier":{"@type":"URI","@value":"https://api.elsevier.com/content/article/PII:S0040402001919982?httpAccept=text/plain"}}],"dc:title":[{"@value":"Homogeneous catalysis in the decomposition of diazo compounds by copper chelates"}],"description":[{"notation":[{"@value":"Abstract   Bis9acetylacetonato)copper(II) catalyzes thermal decomposition of diphenyldiazomethane in benzene to afford tetraphenylethylene and benzophenone azine. The absence of 1,1,2,2-tetraphenylethane among the products is explained by assuming a copper carbenoid in which the carbene moiety is attached to the central copper atom as the fifth ligand. The apparently electrophilic nature of this carbenoid is illustrated by isolating cyclopropylamines upon reaction with enamines. Chemical evidence for the postulated coordination has been obtained by observing several instances of asymmetric synthesis, which proceed under influence of a chiral copper chelate, bis[N-( R )-α-phenethylsalicylaldiminato]copper(II), and its enantiomer. Following products have been obtained in partially resolved form from reactions of methyl or ethyl diazoacetate and diazomethane with appropriate optically inactive substrates: ethyl  cis - and  trans -2-phenylcyclopropanecarboxylate, methyl  cis - and  trans -3-phenyltetrahydrofuran-2-carboxylate,  trans -1-methyl-2-phenylcyclopropane,  trans -bicyclo[10.1.0]- cis -4, trans -8-tridecadiene and  trans -bicyclo[10.1.0]-tridecane. Intramolecular cyclization of allyl diazoacetate and of 1-diazo-6-phenyl- trans -5-hexene-2-one occurs smoothly in the presence of the same copper chelate to afford 3-oxabicyclo[3.1.0]-hexan-2-one and 6-phenylbicyclo[3.1.0]hexan-2-one both in partially resolved state. The mechanism of these carbenoid reactions is discussed on the basis of further additional observations."}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1380569646859982348","@type":"Researcher","foaf:name":[{"@value":"H. Nozaki"}]},{"@id":"https://cir.nii.ac.jp/crid/1383670318857017600","@type":"Researcher","foaf:name":[{"@value":"H. Takaya"}]},{"@id":"https://cir.nii.ac.jp/crid/1383670318857017602","@type":"Researcher","foaf:name":[{"@value":"S. Moriuti"}]},{"@id":"https://cir.nii.ac.jp/crid/1383670318857017728","@type":"Researcher","foaf:name":[{"@value":"R. Noyori"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"00404020"}],"prism:publicationName":[{"@value":"Tetrahedron"}],"dc:publisher":[{"@value":"Elsevier BV"}],"prism:publicationDate":"1968-01","prism:volume":"24","prism:number":"9","prism:startingPage":"3655","prism:endingPage":"3669"},"reviewed":"false","dc:rights":["https://www.elsevier.com/tdm/userlicense/1.0/"],"url":[{"@id":"https://api.elsevier.com/content/article/PII:S0040402001919982?httpAccept=text/xml"},{"@id":"https://api.elsevier.com/content/article/PII:S0040402001919982?httpAccept=text/plain"}],"createdAt":"2002-07-25","modifiedAt":"2019-04-21","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1360002219099914240","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"The Oxidation of Alkylbenzenes and Acylcarbinols by Means of Benzopinacol Diesters"}]},{"@id":"https://cir.nii.ac.jp/crid/1360002219101046912","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Some Aspects on the Mechanism of Palladium-complex-catalyzed Decomposition of and Cyclopropanation with Ethyl Diazoacetate"}]},{"@id":"https://cir.nii.ac.jp/crid/1360002219101907840","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Nickel(0) Catalyzed [2+2] Cross-addition of Bicyclo[2.2.1]heptene Derivatives with Electron-deficient Olefins"}]},{"@id":"https://cir.nii.ac.jp/crid/1360002219108670592","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Enantioselective Construction of Cyclopropane Rings <i>via</i> Asymmetric Simmons-Smith Reaction of Allylic Alcohols"}]},{"@id":"https://cir.nii.ac.jp/crid/1360283691589430272","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Ru(II)–Pheox-Catalyzed Asymmetric Intramolecular Cyclopropanation of Electron-Deficient Olefins"}]},{"@id":"https://cir.nii.ac.jp/crid/1360283694076546816","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"The Reaction of Dicyclopentadiene with Ethyl Diazoacetate"}]},{"@id":"https://cir.nii.ac.jp/crid/1360283694082990336","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"THE NICKEL-CATALYZED ISOMERIZATION OF METHYLENECYCLOPROPANE TO BUTADIENE"}]},{"@id":"https://cir.nii.ac.jp/crid/1360565169052590080","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Cyclic Diacylcarbene Generated from Iodonium Ylides and Diazodiketones"}]},{"@id":"https://cir.nii.ac.jp/crid/1360565169055588352","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Reactions of 2-Diazo-1,2-Diphenylethanone and Diphenyldiazomethane with Ketohydrazones"}]},{"@id":"https://cir.nii.ac.jp/crid/1360565169058187776","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Highly Enantioselective Cyclopropanation of Styrenes and Diazoacetates Catalyzed by 3-Oxobutylideneaminatocobalt(II) Complexes, Part 1. 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