Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes under Acid-Free Conditions: Atom-Economic Synthesis of β,γ-Unsaturated Esters

Carbonylation reactions constitute important methodologies for the synthesis of all kinds of carboxylic acid derivatives. The development of novel and better catalysts for these transformations is of interest for both academic and industrial research. Here, a benign palladium‐based catalyst system f...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2014-08, Vol.53 (34), p.9030-9034
Main Authors: Fang, Xianjie, Li, Haoquan, Jackstell, Ralf, Beller, Matthias
Format: Article
Language:English
Subjects:
carbonylation
conjugation
palladium
P ligands
synthetic methods
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Summary:Carbonylation reactions constitute important methodologies for the synthesis of all kinds of carboxylic acid derivatives. The development of novel and better catalysts for these transformations is of interest for both academic and industrial research. Here, a benign palladium‐based catalyst system for the alkoxycarbonylation of conjugated dienes under acid‐free conditions has been developed. This atom‐efficient transformation provides straightforward access to a variety of β,γ‐unsaturated esters in good to excellent yields and often with high selectivities. As an industrially relevant example the (formal) synthesis of dimethyl adipate and ε‐caprolactam from 1,3‐butadiene is demonstrated. Away with acid: A benign palladium‐based catalyst system for the alkoxycarbonylation of 1,3‐dienes to selectively form β,γ‐unsaturated esters under acid‐free conditions has been developed. This atom‐efficient process is demonstrated in the straightforward synthesis of adipates from 1,3‐butadiene.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201404563