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Updated: Jul 25, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Enantioselective Palladium-Catalyzed Directed Migratory Allylation of Remote Dienes
Xian-Xiao Chen1, Hao Luo1, Ye-Wei Chen1
1CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032, China.
Abstract:
Chain walking has been an efficient route to realize the functionalization of inert C(sp3 )-H bonds, but this strategy is limited to mono-olefin migration and functionalization. Herein, we demonstrate the feasibility of tandem directed simultaneous migrations of remote olefins and stereoselective allylation for the first time. The adoption of palladium hydride catalysis and secondary amine morpholine as solvent is critical for achieving high substrate compatibility and stereochemical control with this method. The protocol is also applicable to the functionalization of three vicinal C(sp3 )-H bonds and thus construct three continuous stereocenters along a propylidene moiety via a short synthetic process. Preliminary mechanistic experiments corroborated the design of simultaneous walking of remote dienes.
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