Regioselectivity of the addition of the highly functionalized zinc‐copper reagents to (η3‐allyl)Fe(CO)4 cationic salts was studied. For 1,1‐disubstituted allyl cation 1, the zinc‐copper reagents added predominantly at the unsubstituted terminus. For 1,1,2‐trisubstituted allyl cation 2, reactive zinc‐copper reagents attacked mainly at the unsubstituted terminus while less reactive zinc‐copper reagents added to a coordinated CO ligand. For 1,1,3‐trisubstituted allyl cation 3, the addition occurred at both the less substituted allyl terminus and a coordinated CO ligand.
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