An efficient synthesis of tetrasubstituted olefins was achieved via a palladium‐catalyzed, chelation‐assisted oxidative Heck arylation protocol from trisubstituted olefins bearing a tether with a directing group in a completely stereo‐ and regioselective manner. The stereo‐ and regioselectivity as well as excellent yields of tetrasubstituted olefins originated from the stabilization of a palladium intermediate by chelation between the palladium center and a directing group.
A practical and efficient synthesis of various 1,2,5-tricarbonyl compounds is described. The synthesis has been carried out by a conjugate addition of methyl cyanoacetate to the b-position of a,b-unsaturated carbonyl compounds and a subsequent copper(I) iodide-catalyzed aerobic oxidation. In addition, various a-aryl-and a-alkyl-a-keto esters have been synthesized using a similar approach.
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