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An Expedient Method for the Umpolung Coupling of Enols with Heteronucleophiles

Authors :
Química orgánica I
Kimika organikoa I
García Vázquez, Víctor
Carretero Cerdán, Alba
Sanz-Marco, Amparo
Gomez Bengoa, Enrique
Martín Matute, Belén
Química orgánica I
Kimika organikoa I
García Vázquez, Víctor
Carretero Cerdán, Alba
Sanz-Marco, Amparo
Gomez Bengoa, Enrique
Martín Matute, Belén
Publication Year :
2022

Abstract

[EN] In this paper, we present an unprecedented and general umpolung protocol that allows the functionalization of silyl enol ethers and of 1,3-dicarbonyl compounds with a large range of heteroatom nucleophiles, including carboxylic acids, alcohols, primary and secondary amines, azide, thiols, and also anionic carbamates derived from CO2. The scope of the reaction also extends to carbon-based nucleophiles. The reaction relies on the use of 1-bromo-3,3-dimethyl-1,3-dihydro-1 lambda(3)[d][1,2]iodaoxole, which provides a key alpha-brominated carbonyl intermediate. The reaction mechanism has been studied experimentally and by DFT, and we propose formation of an unusual enolonium intermediate with a halogen-bonded bromide.

Details

Database :
OAIster
Notes :
The authors are grateful for support from the Swedish Research Council through Vetenskapsradet, and from the Goran Gustafsson Foundation. This project was also funded by the European Union's Horizon 2020 research and innovation programme under Grant Agreement 721223 and NordForsk through NordCO2 (85378)., English
Publication Type :
Electronic Resource
Accession number :
edsoai.on1346951654
Document Type :
Electronic Resource