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

J Org Chem. 2016 Jul 1;81(13):5795-802. doi: 10.1021/acs.joc.6b01306. Epub 2016 Jun 17.

Abstract

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.

Publication types

  • Research Support, Non-U.S. Gov't