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Catalytic asymmetric Nakamura reaction by gold(I)/chiral N,N'-dioxide-indium(III) or nickel(II) synergistic catalysis.

ABSTRACT: Intermolecular addition of enols and enolates to unactivated alkynes was proved to be a simple and powerful method for carbon-carbon bond formation. Up to date, a catalytic asymmetric version of alkyne with 1,3-dicarbonyl compound has not been realized. Herein, we achieve the catalytic asymmetric intermolecular addition of 1,3-dicarbonyl compounds to unactivated 1-alkynes attributing to the synergistic activation of chiral N,N'-dioxide-indium(III) or nickel(II) Lewis acid and achiral gold(I) π-acid. A range of β-ketoamides, β-ketoesters and 1,3-diketones transform to the corresponding products with a tetra-substituted chiral center in good yields with good e.r. values. Besides, a possible catalytic cycle and a transition state model are proposed to illustrate the reaction process and the origin of chiral induction based on the experimental investigations.

SUBMITTER: Hu X

PROVIDER: S-EPMC8140141 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

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Catalytic asymmetric Nakamura reaction by gold(I)/chiral N,N'-dioxide-indium(III) or nickel(II) synergistic catalysis.

Hu Xinyue X Tang Xiaoxue X Zhang Xiying X Lin Lili L Feng Xiaoming X

Nature communications 20210521 1

Intermolecular addition of enols and enolates to unactivated alkynes was proved to be a simple and powerful method for carbon-carbon bond formation. Up to date, a catalytic asymmetric version of alkyne with 1,3-dicarbonyl compound has not been realized. Herein, we achieve the catalytic asymmetric intermolecular addition of 1,3-dicarbonyl compounds to unactivated 1-alkynes attributing to the synergistic activation of chiral N,N'-dioxide-indium(III) or nickel(II) Lewis acid and achiral gold(I) π-a ...[more]

PMID: 34021138

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