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3076165 
Journal Article 
Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes under Acid-Free Conditions: Atom-Economic Synthesis of beta,gamma-Unsaturated Esters 
Fang, X; Li, H; Jackstell, R; Beller, M 
2014 
Yes 
Angewandte Chemie (International Edition)
ISSN: 1433-7851
EISSN: 1521-3773 
53 
34 
9030-9034 
English 
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 beta,gamma-unsaturated esters in good to excellent yields and often with high selectivities. As an industrially relevant example the (formal) synthesis of dimethyl adipate and epsilon-caprolactam from 1,3-butadiene is demonstrated. 
carbonylation; conjugation; P ligands; palladium; synthetic methods