{"@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/1360011144878272000.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1002/hlca.19950780202"}},{"identifier":{"@type":"URI","@value":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fhlca.19950780202"}},{"identifier":{"@type":"URI","@value":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/hlca.19950780202"}},{"identifier":{"@type":"NAID","@value":"30009976871"}}],"dc:title":[{"@value":"Enantioselective Allylic Substitution Catalyzed by Chiral [Bis(dihydrooxazole)]palladium Complexes: Catalyst structure and possible mechanism of enantioselection"}],"description":[{"type":"abstract","notation":[{"@value":"<jats:title>Abstract</jats:title><jats:p>Allylpalladium complexes with chiral bis(dihydrooxazole) ligands were studied as catalysts for the enantioselective allylic substitution reaction of <jats:italic>rac</jats:italic>‐1,3‐diphenylprop‐2‐enyl acetate (<jats:italic>rac</jats:italic>‐<jats:bold>5</jats:bold>) with the anion of dimethyl malonate (<jats:italic>Scheme 1</jats:italic>). Using enantiomerically pure (<jats:italic>S</jats:italic>,<jats:italic>E</jats:italic>)‐1‐(4‐tolyl)‐3‐phenylprop‐2‐enyl acatete ((<jats:italic>S</jats:italic>)‐<jats:bold>25</jats:bold>) as substrate, the reaction was shown to proceed by a clean ‘<jats:italic>syn</jats:italic>’ displacement of acetate by dimethyl malonate (<jats:italic>Scheme 6</jats:italic>). The [Pd<jats:sup>11</jats:sup>(η<jats:sup>3</jats:sup>‐allyl)] complex <jats:bold>18</jats:bold> and the analogous [Pd(η<jats:sup>3</jats:sup>‐1,3‐diphenylallyl)] complex <jats:bold>20</jats:bold>, both containing the same bis(dihydrooxazole) ligand, were characterized by X‐ray structure analysis and by NMR spectroscopy in solution. The structural data reveal that steric interactions of the allyl system with the chiral ligand result in selective electronic activation of one of the allylic termini. The higher reactivity of one allylic terminus toward nucleophilic attack is reflected in a significantly longer PdC bond and a shift of the corresponding <jats:sup>13</jats:sup>C‐NMR resonance to higher frequency.</jats:p>"}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1380011144878272008","@type":"Researcher","foaf:name":[{"@value":"Peter Von Matt"}]},{"@id":"https://cir.nii.ac.jp/crid/1380861293600738560","@type":"Researcher","foaf:name":[{"@value":"Guy C. Lloyd‐Jones"}]},{"@id":"https://cir.nii.ac.jp/crid/1380011144878272004","@type":"Researcher","foaf:name":[{"@value":"Alexander B. E. Minidis"}]},{"@id":"https://cir.nii.ac.jp/crid/1380011144878272001","@type":"Researcher","foaf:name":[{"@value":"Andreas Pfaltz"}]},{"@id":"https://cir.nii.ac.jp/crid/1380011144878272005","@type":"Researcher","foaf:name":[{"@value":"Ludwig Macko"}]},{"@id":"https://cir.nii.ac.jp/crid/1380011144878272006","@type":"Researcher","foaf:name":[{"@value":"Markus Neuburger"}]},{"@id":"https://cir.nii.ac.jp/crid/1380011144878272000","@type":"Researcher","foaf:name":[{"@value":"Margareta Zehnder"}]},{"@id":"https://cir.nii.ac.jp/crid/1380011144878272007","@type":"Researcher","foaf:name":[{"@value":"Heinz Rüegger"}]},{"@id":"https://cir.nii.ac.jp/crid/1380011144878272003","@type":"Researcher","foaf:name":[{"@value":"Paul S. Pregosin"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"0018019X"},{"@type":"EISSN","@value":"15222675"}],"prism:publicationName":[{"@value":"Helvetica Chimica Acta"}],"dc:publisher":[{"@value":"Wiley"}],"prism:publicationDate":"1995-03-22","prism:volume":"78","prism:number":"2","prism:startingPage":"265","prism:endingPage":"284"},"reviewed":"false","dc:rights":["http://onlinelibrary.wiley.com/termsAndConditions#vor"],"url":[{"@id":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fhlca.19950780202"},{"@id":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/hlca.19950780202"}],"createdAt":"2004-12-28","modifiedAt":"2023-10-26","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1360565169062593024","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Molecular Structure of 1,3-Disubstituted <i>π</i>-Allyl Palladium(II) Complexes with a Chiral Diphosphine: The Intermediate of Palladium-catalyzed Asymmetric Allylic Alkylation"}]},{"@id":"https://cir.nii.ac.jp/crid/1360846644039712128","@type":"Article","relationType":["isReferencedBy","isCitedBy"],"jpcoar:relatedTitle":[{"@value":"Enantioselective Nucleophilic Substitution of a 6,6-Bicyclic Dienyl Acetate by Palladium-Chiral Phosphine Catalyst"}]},{"@id":"https://cir.nii.ac.jp/crid/1390001204178333568","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Development of Palladium-Catalyzed Transformations Using Propargylic Compounds"}]},{"@id":"https://cir.nii.ac.jp/crid/1390001205341528576","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"ja","@value":"パラジウム触媒を用いたプロパルギルエステルと求核剤の環化反応による環状化合物の選択的合成"},{"@language":"en","@value":"Selective Synthesis of Cyclic Compounds by Palladium-Catalyzed Cyclization of Propargylic Esters with Nucleophiles"},{"@language":"ja-Kana","@value":"パラジウム ショクバイ オ モチイタ プロパルギルエステル ト キュウカクザイ ノ カンカ ハンノウ ニ ヨル カンジョウ カゴウブツ ノ センタクテキ ゴウセイ"}]},{"@id":"https://cir.nii.ac.jp/crid/1390282679146718976","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Interesting Nickel-Catalyzed 1,2-Addition to .ALPHA.,.BETA.-Unsaturated Aldehydes with Arylborates"},{"@value":"ChemInform Abstract: Interesting Nickel‐Catalyzed 1,2‐Addition to α,β‐Unsaturated Aldehydes with Arylborates."}]},{"@id":"https://cir.nii.ac.jp/crid/1390282680287715712","@type":"Article","relationType":["isCitedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Development of the First Spiro Bis (isoxazoline) Ligands (SPRIXs) and Their Applications to Catalytic Enantioselective Reactions"},{"@value":"スピロビスイソオキサゾリン配位子 (SPRIXs) の創製と触媒的不斉合成への応用"},{"@language":"ja-Kana","@value":"スピロビスイソオキサゾリン ハイイシ SPRIXs ノ ソウセイ ト ショクバイテキ フセイ ゴウセイ エ ノ オウヨウ"}]},{"@id":"https://cir.nii.ac.jp/crid/2050025942155224064","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Research on the efficient enantioselective total synthesis of useful bioactive polycyclic compounds"}]}],"dataSourceIdentifier":[{"@type":"CROSSREF","@value":"10.1002/hlca.19950780202"},{"@type":"CIA","@value":"30009976871"},{"@type":"CROSSREF","@value":"10.1248/cpb.60.285_references_DOI_9ToBVeP8eq3PUnGL2ohuTFUgl0A"},{"@type":"CROSSREF","@value":"10.1246/bcsj.20210329_references_DOI_9ToBVeP8eq3PUnGL2ohuTFUgl0A"},{"@type":"CROSSREF","@value":"10.1248/cpb.57.511_references_DOI_9ToBVeP8eq3PUnGL2ohuTFUgl0A"},{"@type":"CROSSREF","@value":"10.1246/cl.1998.983_references_DOI_9ToBVeP8eq3PUnGL2ohuTFUgl0A"},{"@type":"CROSSREF","@value":"10.1246/cl.1996.241_references_DOI_9ToBVeP8eq3PUnGL2ohuTFUgl0A"},{"@type":"CROSSREF","@value":"10.5059/yukigoseikyokaishi.75.38_references_DOI_9ToBVeP8eq3PUnGL2ohuTFUgl0A"}]}