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Updated: Oct 25, 2025
Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Asymmetric Aminomethylative Etherification of Conjugated Dienes with Aliphatic Alcohols Facilitated by Hydrogen
Rui Chang1, Shoule Cai1, Guoqing Yang1
1Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, Center for Excellence in Molecular Synthesis of CAS, University of Science and Technology of China, Hefei, 230026, People's Republic of China.
Abstract:
The asymmetric construction of allylic C-O bonds with primary or secondary aliphatic alcohols remains a substantial challenge in Pd-catalyzed allylation chemistry. Here, we report the development of an additive-free, palladium-catalyzed asymmetric aminomethylative etherification of conjugated dienes that enables the efficient, asymmetric O-allylation of primary and secondary aliphatic alcohols as well as water. Mechanism studies revealed that the hydrogen-bonding interaction between the alcohol and the in situ introduced aminomethyl moiety is critical to facilitate the nucleophilic addition of the alcohol to the π-allylpalladium species, which opened up the possibility of using aliphatic alcohols and water as nucleophilic substrates. This reaction tolerates a broad range of functional groups and shows remarkable regioselectivities and uniformly high enantioselectivities, which provides a direct and rapid approach to optically pure allylic 1,3-amino ethers and 1,3-amino alcohols from simple starting materials.
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