{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,12,30]],"date-time":"2025-12-30T23:22:37Z","timestamp":1767136957561,"version":"build-2238731810"},"reference-count":27,"publisher":"Wiley","issue":"36","license":[{"start":{"date-parts":[[2009,11,11]],"date-time":"2009-11-11T00:00:00Z","timestamp":1257897600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Eur J Org Chem"],"published-print":{"date-parts":[[2009,12]]},"abstract":"Abstract<\/jats:title>\n \n A relatively unexploited commercial ligand, (\n R<\/jats:italic>\n ,\n R<\/jats:italic>\n )\u2010DUPHOS\u2010\n i<\/jats:italic>\n Pr (\n 1b<\/jats:bold>\n ) was tested in the Pd\n 0<\/jats:sup>\n \u2010catalysed asymmetric allylic alkyation reaction using\n rac<\/jats:italic>\n \u20101,3\u2010diphenylpropenyl acetate as substrate, malonate as nucleophile and a variety of Pd pre\u2010catalysts under standard conditions. Excellent\n ee<\/jats:italic>\n values (up to \u2265 98\u2009%) could be obtained with\n 1b<\/jats:bold>\n , but the conversions were generally inferior to those obtained using (\n R<\/jats:italic>\n ,\n R<\/jats:italic>\n )\u2010Me\u2010DUPHOS (\n 1a<\/jats:bold>\n ) under similar conditions. It was also observed that there was a switch in the absolute configuration of the malonate product to (R) on using\n 1b<\/jats:bold>\n to form the catalyst. This was an indication of the complementary nature of these two ligands. In order to explain this, a rigorous detailed semi\u2010emperical computational study was undertaken. DFT calculations of the Fukui Function (FF) were also conducted to confirm the most likely site (electrophilic) for nucleophilic attack on the active Pd\u2010allyl complex. In the case of the Pd catalyst formed with\n 1b<\/jats:bold>\n . This result indicated that stereochemical factors were more important than electronic factors in this reaction with\n 1b<\/jats:bold>\n . Kinetic studies were also conducted to compare the activities of the catalysts\n 2a<\/jats:bold>\n and\n 2b<\/jats:bold>\n formed with (\n R<\/jats:italic>\n ,\n R<\/jats:italic>\n )\u2010Me\u2010DUPHOS (\n 1a<\/jats:bold>\n ) and (\n R<\/jats:italic>\n ,\n R<\/jats:italic>\n )\u2010DUPHOS\u2010\n i<\/jats:italic>\n Pr (\n 1b<\/jats:bold>\n ).(\u00a9 Wiley\u2010VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)\n <\/jats:p>","DOI":"10.1002\/ejoc.200900649","type":"journal-article","created":{"date-parts":[[2009,12,1]],"date-time":"2009-12-01T14:46:25Z","timestamp":1259678785000},"page":"6311-6317","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["A Comparison of (\n R<\/i>\n ,\n R<\/i>\n )\u2010Me\u2010DUPHOS and (\n R<\/i>\n ,\n R<\/i>\n )\u2010DUPHOS\u2010\n i<\/i>\n Pr Ligands in the Pd\n 0<\/sup>\n \u2010Catalysed Asymmetric Allylic Alkylation Reaction: Stereochemical and Kinetic Considerations"],"prefix":"10.1002","volume":"2009","author":[{"given":"Vanda Raquel","family":"Marinho","sequence":"first","affiliation":[]},{"given":"J. P. Prates","family":"Ramalho","sequence":"additional","affiliation":[]},{"given":"Ana I.","family":"Rodrigues","sequence":"additional","affiliation":[]},{"given":"Anthony J.","family":"Burke","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2009,12]]},"reference":[{"key":"e_1_2_6_1_2","volume-title":"Catalytic Asymmetric Synthesis","author":"Trost B. M.","year":"2000"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00447a064"},{"key":"e_1_2_6_3_2","unstructured":""},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetasy.2007.07.004"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1080\/00397910802323106"},{"key":"e_1_2_6_6_2","unstructured":"V. M. Marinho A. J. Burke Synth. 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