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- Title
An Expedient Method for the Umpolung Coupling of Enols with Heteronucleophiles**.
- Authors
García‐Vázquez, Víctor; Carretero Cerdán, Alba; Sanz‐Marco, Amparo; Gómez‐Bengoa, Enrique; Martín‐Matute, Belén
- Abstract
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‐1λ3[d][1,2]iodaoxole, which provides a key α‐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.
- Subjects
UMPOLUNG; ENOLS; SILYL enol ethers; NUCLEOPHILES; SECONDARY amines; ENOL ethers; ALCOHOL
- Publication
Chemistry - A European Journal, 2022, Vol 28, Issue 44, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202201000