Allenes as Carbon Nucleophiles in Intramolecular Attack on (π‐1,3‐Diene)palladium Complexes: Evidence for trans Carbopalladation of the 1,3‐Diene
Authors:
- 11 July 2003
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 9 (14) , 3445-3449
Abstract
Reaction of allene‐substituted cyclohexa‐ and cyclohepta‐1,3‐dienes with [PdCl2(PhCN)2] gave η3‐(1,2,3)‐cyclohexenyl‐ and η3‐(1,2,3)‐cycloheptenylpalladium complexes, respectively, in which CC bond formation between the allene and the 1,3‐diene has occurred. Analysis of the (π‐allyl)palladium complexes by NMR spectroscopy, using reporter ligands, shows that the CC bond formation has occurred by a trans carbopalladation involving nucleophilic attack by the middle carbon atom of the allene on a (π‐diene)palladium(II) complex. The stereochemistry of the (π‐allyl)palladium complexes was confirmed by benzoquinone‐induced stereoselective transformations to allylic acetates.Keywords
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