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An umpolung strategy to react catalytic enols with nucleophiles
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry. Universidad del PaísVasco/UPV-EHU, Spain.
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Number of Authors: 52019 (English)In: Nature Communications, ISSN 2041-1723, E-ISSN 2041-1723, Vol. 10, article id 5244Article in journal (Refereed) Published
Abstract [en]

The selective synthesis of a-functionalized ketones with two similar enolizable positions can be accomplished using allylic alcohols and iridium(III) catalysts. A formal 1,3-hydrogen shift on allylic alcohols generates catalytic iridium-enolates in a stereospecific manner, which are able to react with electrophiles to yield alpha-functionalized ketones as single constitutional isomers. However, the employment of nucleophiles to react with the nucleophilic catalytic enolates in this chemistry is still unknown. Herein, we report an umpolung strategy for the selective synthesis of alpha-alkoxy carbonyl compounds by the reaction of iridium enolates and alcohols promoted by an iodine(III) reagent. Moreover, the protocol also works in an intra-molecular fashion to synthesize 3(2H)-furanones from gamma-keto allylic alcohols. Experimental and computational investigations have been carried out, and mechanisms are proposed for both the inter- and intramolecular reactions, explaining the key role of the iodine(III) reagent in this umpolung approach.

Place, publisher, year, edition, pages
2019. Vol. 10, article id 5244
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Chemical Sciences
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URN: urn:nbn:se:su:diva-176494DOI: 10.1038/s41467-019-13175-5ISI: 000497694100012PubMedID: 31748504OAI: oai:DiVA.org:su-176494DiVA, id: diva2:1381761
Available from: 2019-12-27 Created: 2019-12-27 Last updated: 2019-12-27Bibliographically approved

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Sanz-Marco, AmparoMartinez-Erro, SamuelPauze, MartinMartín-Matute, Belén
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