Regioselective γ-polyhaloalkylation is achieved using tetrahalomethanes or α,α,α-trihaloalkyl compounds and siloxydienes via Fe(II) catalysis. A range of siloxydienes are functionalized in good yields with high stereoselectivity under mild reaction conditions. Structural divergence is observed as either haloalkylated or haloalkenylated products are formed on the basis of the substitution pattern of the siloxydiene.
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