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γ‑Selective Allylation of (E)‑Alkenylzinc Iodides Prepared by Reductive Coupling of Arylacetylenes with Alkyl Iodides

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journal contribution
posted on 2016-06-10, 00:00 authored by Fedor E. Zhurkin, Xile Hu
The first examples of Cu-catalyzed γ-selective allylic alkenylation using organozinc reagents are reported. (E)-Alkenylzinc iodides were prepared by Fe-catalyzed reductive coupling of terminal arylalkynes with alkyl iodides. In the presence of a copper catalyst, these reagents reacted with allylic bromides derived from Morita–Baylis–Hillman alcohols to give 1,4-dienes in high yields. The reactions are highly γ-selective (generally γ/α > 49:1) and tolerate a wide range of functional groups such as ester, cyano, keto, and nitro.