This presentation details the development of nickel-catalyzed carboacylation of <i>ortho</i>-allylbenzamides with arylboronic acid pinacol esters to form 2-benzyl-2,3-dihydro-1<i>H</i>-inden-1-ones in up to 99% yield. These reactions represent the first examples of alkene carboacylation initiated by activation of amide C-N bonds and enable the difunctionalization of alkenes through the formation of two new carbon-carbon bonds. Preliminary mechanistic data supporting a sequence of elementary steps initiated by nickel-mediated activation of the amide C-N bond followed by transmetalation, migratory insertion, and reductive elimination will also be presented. The synthetic utility of this carboacylation reaction will be demonstrated with the development of a gram-scale reaction and by sequencing with nickel-catalyzed enantioselective α-arylation to form indanone derivatives containing a quaternary sterogenic center.

Amide bond activation as an entry to alkene carboacylation

255th National Meeting (2018)

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