An umpolung strategy to react catalytic enols with nucleophiles

Amparo Sanz-Marco, Samuel Martinez-Erro, Martin Pauze, Enrique Gómez-Bengoa and Belén Martín-Matute ()
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Amparo Sanz-Marco: Stockholm University
Samuel Martinez-Erro: Stockholm University
Martin Pauze: Stockholm University
Enrique Gómez-Bengoa: Universidad del País Vasco/UPV-EHU
Belén Martín-Matute: Stockholm University

Nature Communications, 2019, vol. 10, issue 1, 1-9

Abstract: Abstract The selective synthesis of α-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 α-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 α-alkoxy carbonyl compounds by the reaction of iridium enolates and alcohols promoted by an iodine(III) reagent. Moreover, the protocol also works in an intramolecular fashion to synthesize 3(2H)-furanones from γ-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.

Date: 2019
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Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:10:y:2019:i:1:d:10.1038_s41467-019-13175-5

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DOI: 10.1038/s41467-019-13175-5

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