Nickel-Catalyzed β-Carboxylation of Ynamides with Carbon Dioxide
A nickel-catalyzed β-selective hydrocarboxylation of ynamides to give protected dehydro-β-amino acids was developed. The key to exclusive β-selectivity was the use of diethylzinc as a reductant in the presence of a magnesium salt. The reaction was conducted with bis(acetylacetonato)nickel(II) instead of costly and sensitive bis(1,5-cyclooctadiene)nickel(0). In addition, the optimized ligand was inexpensive 1,5-cyclooctadiene. Investigation of the substrate scope revealed that both nitrogen and alkyne substituents have marked effects on the reaction efficiency. We obtained experimental clues that indicated the formation of a vinylzinc intermediate that forms a C–C bond with CO2.
1943 ◽
Vol 150
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pp. 231-250
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2003 ◽
Vol 81
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pp. 1333-1342
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2016 ◽
Vol 4
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pp. 3170-3176
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1961 ◽
Vol 39
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pp. 1717-1735
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1963 ◽
Vol 41
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pp. 737-743
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