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Stereoselective allyl isomerization and regiospecific allyl arylation reactions of allylarenes with a catalytic system comprising nickel(II) with an aryl Grignard reagent were studied. Both reactions are triggered by allylic internal C(sp2)–H activation by in‐situ‐formed Ni0, which is inserted into the C–H bond at the 2‐position of the allyl moiety without a directing group. The isomerization of allylarene...
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