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Evidence for a Non‐Concerted, Dissoziative Mechanism of the Palladium‐Catalyzed “Enolate Claisen Rearrangement” of Allylic Esters
Author(s) -
Braun Manfred,
Meletis Panos,
Schrader Wolfgang
Publication year - 2010
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201000874
Subject(s) - chemistry , palladium , claisen rearrangement , allylic rearrangement , sigmatropic reaction , carroll rearrangement , deprotonation , concerted reaction , catalysis , reaction mechanism , cope rearrangement , pericyclic reaction , carboxylic acid , medicinal chemistry , enantioselective synthesis , organic chemistry , stereochemistry , ion
In an enolate Claisen rearrangement, deprotonated allyl phenylacetate undergoes a smooth conversion at –78 °C to 2‐phenyl‐4‐pentenoic acid under palladium(0) catalysis. By using labelled starting materials in crossover experiments, the reaction is shown to follow a dissoziative, non‐concerted, non‐[3,3]‐sigmatropic mechanism that involves palladium complexes and carboxylic‐acid dianions as intermediates.