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Palladium‐Catalyzed Aminocarbonylation of Allylic Alcohols
Author(s) -
Li Haoquan,
Neumann Helfried,
Beller Matthias
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601260
Subject(s) - allylic rearrangement , palladium , chemistry , carbonylation , catalysis , xantphos , organic chemistry , amination , ligand (biochemistry) , triphenylphosphine , amide , steric effects , reactivity (psychology) , combinatorial chemistry , medicinal chemistry , carbon monoxide , medicine , biochemistry , receptor , alternative medicine , pathology
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 PdCl 2 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.