{"@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/1361699995368781184.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1002/anie.201804197"}},{"identifier":{"@type":"URI","@value":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.201804197"}},{"identifier":{"@type":"URI","@value":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201804197"}}],"dc:title":[{"@value":"Palladium(II)‐Catalyzed Enantioselective Arylation of Unbiased Methylene C(sp<sup>3</sup>)−H Bonds Enabled by a 2‐Pyridinylisopropyl Auxiliary and Chiral Phosphoric Acids"}],"description":[{"type":"abstract","notation":[{"@value":"<jats:title>Abstract</jats:title><jats:p>Enantioselective functionalizations of unbiased methylene C(sp<jats:sup>3</jats:sup>)−H bonds of linear systems by metal insertion are intrinsically challenging and remain a largely unsolved problem. Herein, we report a palladium(II)‐catalyzed enantioselective arylation of unbiased methylene β‐C(sp<jats:sup>3</jats:sup>)−H bonds enabled by the combination of a strongly coordinating bidentate PIP auxiliary with a monodentate chiral phosphoric acid (CPA). The synergistic effect between the PIP auxiliary and the non‐<jats:italic>C</jats:italic><jats:sub>2</jats:sub>‐symmetric CPA is crucial for effective stereocontrol. A broad range of aliphatic carboxylic acids and aryl bromides can be used, providing β‐arylated aliphatic carboxylic acid derivatives in high yields (up to 96 %) with good enantioselectivities (up to 95:5 e.r.). Notably, this reaction also represents the first palladium(II)‐catalyzed enantioselective C−H activation with less reactive and cost‐effective aryl bromides as the arylating reagents. Mechanistic studies suggest that a single CPA is involved in the stereodetermining C−H palladation step.</jats:p>"}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1380861295268327552","@type":"Researcher","foaf:name":[{"@value":"Sheng‐Yi Yan"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry Zhejiang University  Hangzhou 310027 China"}]},{"@id":"https://cir.nii.ac.jp/crid/1380861295268327555","@type":"Researcher","foaf:name":[{"@value":"Ye‐Qiang Han"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry Zhejiang University  Hangzhou 310027 China"}]},{"@id":"https://cir.nii.ac.jp/crid/1380861295268327554","@type":"Researcher","foaf:name":[{"@value":"Qi‐Jun Yao"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry Zhejiang University  Hangzhou 310027 China"}]},{"@id":"https://cir.nii.ac.jp/crid/1380861295268327553","@type":"Researcher","foaf:name":[{"@value":"Xing‐Liang Nie"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry Zhejiang University  Hangzhou 310027 China"}]},{"@id":"https://cir.nii.ac.jp/crid/1381699995368781189","@type":"Researcher","foaf:name":[{"@value":"Lei Liu"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry Zhejiang University  Hangzhou 310027 China"}]},{"@id":"https://cir.nii.ac.jp/crid/1380861295268327556","@type":"Researcher","foaf:name":[{"@value":"Bing‐Feng Shi"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry Zhejiang University  Hangzhou 310027 China"},{"@value":"State Key Laboratory of Elemento-organic Chemistry Nankai University  Tianjin 300071 China"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"14337851"},{"@type":"EISSN","@value":"15213773"}],"prism:publicationName":[{"@value":"Angewandte Chemie International Edition"}],"dc:publisher":[{"@value":"Wiley"}],"prism:publicationDate":"2018-06-19","prism:volume":"57","prism:number":"29","prism:startingPage":"9093","prism:endingPage":"9097"},"reviewed":"false","dc:rights":["http://onlinelibrary.wiley.com/termsAndConditions#vor"],"url":[{"@id":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.201804197"},{"@id":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201804197"}],"createdAt":"2018-05-28","modifiedAt":"2023-09-17","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1050306506452363520","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Chiral Carboxylic Acid Enabled Achiral Rhodium(III)-Catalyzed Enantioselective C-H Functionalization"},{"@value":"Chiral Carboxylic Acid Enabled Achiral Rhodium(III)‐Catalyzed Enantioselective C−H 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Catalysts"}]},{"@id":"https://cir.nii.ac.jp/crid/1360853567696816896","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Palladium‐Catalyzed Secondary C(<i>sp</i><sup>3</sup>)−H Arylation of 2‐Alkylpyridines"}]},{"@id":"https://cir.nii.ac.jp/crid/1360861707119504128","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Desymmetrization of prochiral methylenes by asymmetric chain-walking cyclization using bioxazoline palladium catalysts"}]},{"@id":"https://cir.nii.ac.jp/crid/1361975842823746176","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C 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