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Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts
Published on: February 24, 2015
Rh-catalyzed alkoxycarbonylation of unactivated alkyl chlorides
Peng Wang1, Yaxin Wang1, Helfried Neumann1
1Leibniz-Institut für Katalyse e. V. Albert-Einstein-Straße 29a Rostock 18059 Germany helfried.neumann@catalysis.de matthias.beller@catalysis.de.
Abstract:
A general rhodium-catalyzed selective carbonylative coupling of unactivated alkyl chlorides with aliphatic alcohols or phenols to the corresponding esters is presented for the first time. Crucial for this transformation is the addition of sodium iodide, which provides in situ more active alkyl iodides. In the presence of a Rh(i)-DPPP catalyst system diverse esters (81 examples) including industrially relevant acetates from chloro- and dichloromethane can be prepared in a straightforward manner in up to 95% isolated yield. The used ligand not only affects the selectivity of the carbonylation reaction but also controls the selectivity of the preceding halide exchange step.
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