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- Title
An umpolung strategy to react catalytic enols with nucleophiles.
- Authors
Sanz-Marco, Amparo; Martinez-Erro, Samuel; Pauze, Martin; Gómez-Bengoa, Enrique; Martín-Matute, Belén
- 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. Nucleophiles cannot be directly reacted with enolates due to polarity mismatching. Here, the authors developed an umpolung strategy for the selective synthesis of α-alkoxy carbonyl compounds by reaction of iridium enolates with nucleophilic alcohols promoted by an iodine(III) reagent.
- Subjects
UMPOLUNG; NUCLEOPHILES; KETONES; ALLYL alcohol; CATALYSTS; CARBONYL compounds
- Publication
Nature Communications, 2019, Vol 10, Issue 1, pN.PAG
- ISSN
2041-1723
- Publication type
Article
- DOI
10.1038/s41467-019-13175-5