{"@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/1361699995883080064.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1002/anie.201508817"}},{"identifier":{"@type":"URI","@value":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.201508817"}},{"identifier":{"@type":"URI","@value":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201508817"}},{"identifier":{"@type":"URI","@value":"https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.201508817"}},{"identifier":{"@type":"URI","@value":"https://onlinelibrary.wiley.com/doi/am-pdf/10.1002/anie.201508817"}}],"dc:title":[{"@value":"Myoglobin‐Catalyzed Olefination of Aldehydes"}],"description":[{"type":"abstract","notation":[{"@value":"<jats:title>Abstract</jats:title><jats:p>The olefination of aldehydes constitutes a most valuable and widely adopted strategy for constructing carbon–carbon double bonds in organic chemistry. While various synthetic methods have been made available for this purpose, no biocatalysts are known to mediate this transformation. Reported herein is that engineered myoglobin variants can catalyze the olefination of aldehydes in the presence of α‐diazoesters with high catalytic efficiency (up to 4,900 turnovers) and excellent <jats:italic>E</jats:italic> diastereoselectivity (92–99.9 % <jats:italic>de</jats:italic>). This transformation could be applied to the olefination of a variety of substituted benzaldehydes and heteroaromatic aldehydes, also in combination with different alkyl α‐diazoacetate reagents. This work provides a first example of biocatalytic aldehyde olefination and extends the spectrum of synthetically valuable chemical transformations accessible using metalloprotein‐based catalysts.</jats:p>"}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1381699995883080064","@type":"Researcher","foaf:name":[{"@value":"Vikas Tyagi"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry University of Rochester  120 Trustee Road Rochester NY 14627 USA"}]},{"@id":"https://cir.nii.ac.jp/crid/1381699995883080065","@type":"Researcher","foaf:name":[{"@value":"Rudi Fasan"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry University of Rochester  120 Trustee Road Rochester NY 14627 USA"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"14337851"},{"@type":"EISSN","@value":"15213773"}],"prism:publicationName":[{"@value":"Angewandte Chemie International Edition"}],"dc:publisher":[{"@value":"Wiley"}],"prism:publicationDate":"2016-01-14","prism:volume":"55","prism:number":"7","prism:startingPage":"2512","prism:endingPage":"2516"},"reviewed":"false","dc:rights":["http://onlinelibrary.wiley.com/termsAndConditions#am","http://onlinelibrary.wiley.com/termsAndConditions#vor"],"url":[{"@id":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.201508817"},{"@id":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201508817"},{"@id":"https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.201508817"},{"@id":"https://onlinelibrary.wiley.com/doi/am-pdf/10.1002/anie.201508817"}],"createdAt":"2016-01-14","modifiedAt":"2023-10-06","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1050019590267566464","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Redox Engineering of Myoglobin by Cofactor Substitution to Enhance Cyclopropanation Reactivity"}]},{"@id":"https://cir.nii.ac.jp/crid/1360285708125891328","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"A Phosphonium Ylide as an Ionic Nucleophilic Catalyst for Primary Hydroxyl Group Selective Acylation of Diols"}]},{"@id":"https://cir.nii.ac.jp/crid/1360289631653244800","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Olefination of Aldehydes with Ethyl Diazoacetate Catalyzed by Nitrogen-doped Carbon-supported Metal"}]},{"@id":"https://cir.nii.ac.jp/crid/1360298757195928192","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Engineering of hemoproteins"}]},{"@id":"https://cir.nii.ac.jp/crid/1360572092633557632","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Myoglobins engineered with artificial cofactors serve as artificial metalloenzymes and models of natural enzymes"}]},{"@id":"https://cir.nii.ac.jp/crid/2050870367081136768","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Exploring and adapting the molecular selectivity of artificial metalloenzymes"}]}],"dataSourceIdentifier":[{"@type":"CROSSREF","@value":"10.1002/anie.201508817"},{"@type":"CROSSREF","@value":"10.1246/bcsj.20200316_references_DOI_CtIiYbeIBw33T1PCRHgAhaGGFtu"},{"@type":"CROSSREF","@value":"10.1246/cl.210355_references_DOI_CtIiYbeIBw33T1PCRHgAhaGGFtu"},{"@type":"CROSSREF","@value":"10.1016/b978-0-12-823144-9.00142-4_references_DOI_CtIiYbeIBw33T1PCRHgAhaGGFtu"},{"@type":"CROSSREF","@value":"10.1002/anie.202403485_references_DOI_CtIiYbeIBw33T1PCRHgAhaGGFtu"},{"@type":"CROSSREF","@value":"10.1039/d0dt03597a_references_DOI_CtIiYbeIBw33T1PCRHgAhaGGFtu"},{"@type":"CROSSREF","@value":"10.1021/acscatal.7b02281_references_DOI_CtIiYbeIBw33T1PCRHgAhaGGFtu"}]}