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Updated: Mar 17, 2026

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Regioselective Transition-Metal-Free Allyl-Allyl Cross-Couplings
Mario Ellwart1, Ilya S Makarov1, Florian Achrainer1
1Ludwig-Maximilians-Universität München, Department Chemie, Butenandtstrasse 5-13, Haus F, 81377, München, Germany.
Abstract:
Readily prepared allylic zinc halides undergo SN 2-type substitutions with allylic bromides in a 1:1 mixture of THF and DMPU providing 1,5-dienes regioselectively. The allylic zinc species reacts at the most branched end (γ-position) of the allylic system furnishing exclusively γ,α'-allyl-allyl cross-coupling products. Remarkably, the double bond stereochemistry of the allylic halide is maintained during the cross-coupling process. Also several functional groups (ester, nitrile) are tolerated. This cross-coupling of allylic zinc reagents can be extended to propargylic and benzylic halides. DFT calculations show the importance of lithium chloride in this substitution.
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