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Catalytic enantioselective allene–anhydride approach to β,γ-unsaturated enones bearing an α-all-carbon-quarternary center
A protocol of highly regio- and enantioselective copper-catalyzed hydroacylation of the non-terminal C[double bond, length as m-dash]C bond in 1,1-disubstituted terminal allenes with anhydrides has been developed. Both aromatic and aliphatic carboxylic anhydrides are applicable to the efficient cons...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8161143/ https://www.ncbi.nlm.nih.gov/pubmed/34094192 http://dx.doi.org/10.1039/d0sc03227a |
Sumario: | A protocol of highly regio- and enantioselective copper-catalyzed hydroacylation of the non-terminal C[double bond, length as m-dash]C bond in 1,1-disubstituted terminal allenes with anhydrides has been developed. Both aromatic and aliphatic carboxylic anhydrides are applicable to the efficient construction of all carbon quarternary centers connected with a versatile C[double bond, length as m-dash]C bond and a useful ketone functionality. The synthetic potentials of the enantioenriched products have also been demonstrated. Density functional theory (DFT) calculations were performed to explain the steric outcome of the products: the hydroacylation proceeds through a six-membered transition state and the ligand-substrate steric interactions account for the observed enantioselectivity although the chiral ligand is far away from the to-be-genetated chiral center. |
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