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The syn / anti ‐Dichotomy in the Palladium‐Catalyzed Addition of Nucleophiles to Alkenes
Author(s) -
Kočovský Pavel,
Bäckvall JanE.
Publication year - 2015
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.201404070
Subject(s) - nucleophile , chemistry , palladium , intramolecular force , catalysis , olefin fiber , wacker process , medicinal chemistry , ethylene , organic chemistry , photochemistry
In this review the stereochemistry of palladium‐catalyzed addition of nucleophiles to alkenes is discussed, and examples of these reactions in organic synthesis are given. Most of the reactions discussed involve oxygen and nitrogen nucleophiles; the Wacker oxidation of ethylene has been reviewed in detail. An anti ‐hydroxypalladation in the Wacker oxidation has strong support from both experimental and computational studies. From the reviewed material it is clear that anti ‐addition of oxygen and nitrogen nucleophiles is strongly favored in intermolecular addition to olefin–palladium complexes even if the nucleophile is coordinated to the metal. On the other hand, syn ‐addition is common in the case of intramolecular oxy‐ and amidopalladation as a result of the initial coordination of the internal nucleophile to the metal.