The syn/anti‐Dichotomy in the Palladium‐Catalyzed Addition of Nucleophiles to Alkenes |
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| Authors: | Prof?Dr Pavel Ko?ovský Prof?Dr Jan‐E Bäckvall |
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| Affiliation: | 1. Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 10691 Stockholm (Sweden), Fax: (+46)?8‐154‐908;2. Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 16610 Prague 6 (Czech Republic);3. Department of Organic Chemistry, Charles University, Hlavova 8, 12843 Prague 2 (Czech Republic) |
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| Abstract: | 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. |
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| Keywords: | alkenes catalysis nucleophilic addition palladium stereochemistry |
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