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Issue 12, 2016
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Nickel-catalyzed alkyl-zincation and carboxylation of diynes

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Abstract

A nickel-catalyzed three-component carbo-carboxylation of aryl-substituted diynes with ZnR2 and CO2 is described. With an ortho-ester functionality in the aryl group as the directing group, the usually observed hydrocarboxylation is completely suppressed with an unexpected C[double bond, length as m-dash]C bond isomerization. Based on the X-ray diffraction analysis and mechanistic study, it is believed that the reaction started with the oxidative addition with an aryl-substituted C–C triple bond and transmetalation with dialkyl zinc, followed by syn-carbonickelation with an alkyl-substituted C–C triple bond. Subsequent reductive elimination afforded the corresponding sp2-carbon zinc intermediate. Finally, the dynamic isomerization of a zinc-linked C[double bond, length as m-dash]C bond and the subsequent exclusive reaction of an isomerized sp2-carbon zinc intermediate with CO2 afforded the final carboxylic acids with a high stereoselectivity.

Graphical abstract: Nickel-catalyzed alkyl-zincation and carboxylation of diynes

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Publication details

The article was received on 23 Aug 2016, accepted on 07 Oct 2016 and first published on 08 Oct 2016


Article type: Research Article
DOI: 10.1039/C6QO00484A
Citation: Org. Chem. Front., 2016,3, 1711-1715
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    Nickel-catalyzed alkyl-zincation and carboxylation of diynes

    T. Cao and S. Ma, Org. Chem. Front., 2016, 3, 1711
    DOI: 10.1039/C6QO00484A

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