Herein, an iron-catalyzed acylation-functionalization of unactivated alkenes with aldehydes via distal group ipso-migration is reported. This strategy overcame the energy barrier and reversibility in the difunctionalization of unactivated alkenes with nucleophilic acyl radicals, and a variety of beta-heteroarylated, -cyanated and -oximated unsymmetrical 1,6- and 1,7-diketones were obtained regioselectively, chemoselectively and efficiently.
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