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Allenes as Carbon Nucleophiles in Intramolecular Attack on (π‐1,3‐Diene)palladium Complexes: Evidence for trans Carbopalladation of the 1,3‐Diene
Author(s) -
Dorange Ismet,
Löfstedt Joakim,
Närhi Katja,
Franzén Johan,
Bäckvall JanE.
Publication year - 2003
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305056
Subject(s) - allene , diene , chemistry , palladium , allylic rearrangement , nucleophile , intramolecular force , medicinal chemistry , stereoselectivity , stereochemistry , catalysis , organic chemistry , natural rubber
Reaction of allene‐substituted cyclohexa‐ and cyclohepta‐1,3‐dienes with [PdCl 2 (PhCN) 2 ] gave η 3 ‐(1,2,3)‐cyclohexenyl‐ and η 3 ‐(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.