Palladium-Catalyzed Aminocarbonylation of Allylic Alcohols.
A benign and efficient palladium-catalyzed aminocarbonylation reaction of allylic alcohols is presented. The generality of this novel process is demonstrated by the synthesis of β,γ-unsaturated amides including aliphatic, cinnamyl, and terpene derivatives. The choice of ligand is crucial for optimal carbonylation processes: Whereas in most cases the combination of PdCl2 with Xantphos (L6) gave best results, sterically hindered substrates performed better in the presence of simple triphenylphosphine (L10), and primary anilines gave the best results using cataCXium® PCy (L8). The reactivity of the respective catalyst system is significantly enhanced by addition of small amounts of water. Mechanistic studies and control experiments revealed a tandem allylic alcohol amination/C-N bond carbonylation reaction sequence.
Leibniz-Institut für Katalyse e. V. an der Universität Rostock, (LIKAT Rostock), Albert-Einstein-Str. 29a, Rostock, 18059, Germany.
Haoquan
H
Li
Leibniz-Institut für Katalyse e. V. an der Universität Rostock, (LIKAT Rostock), Albert-Einstein-Str. 29a, Rostock, 18059, Germany.
Helfried
H
Neumann
Leibniz-Institut für Katalyse e. V. an der Universität Rostock, (LIKAT Rostock), Albert-Einstein-Str. 29a, Rostock, 18059, Germany. Matthias.Beller@catalysis.de.
Matthias
http://orcid.org/0000-0001-5709-0965
M
Beller
allylic; amide; carbonylation; homogeneous catalysis; palladium