Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance upgrade on Thursday 4th of May 2017 from 8.00am to 9.00am (BST).

During this time our websites will be offline temporarily. If you have any questions please use the feedback button on this page. We apologise for any inconvenience this might cause and thank you for your patience.

Issue 12, 2016
Previous Article Next Article

Nickel-catalyzed alkyl-zincation and carboxylation of diynes

Author affiliations


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

Back to tab navigation
Please wait while Download options loads

Supplementary files

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
  •   Request permissions

    Nickel-catalyzed alkyl-zincation and carboxylation of diynes

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

Search articles by author