The syn/anti-Dichotomy in the Palladium-Catalyzed Addition of Nucleophiles to Alkenes

0443145 - ÚOCHB 2016 RIV DE eng J - Článek v odborném periodiku
Kočovský, Pavel - Bäckvall, J. E.
The syn/anti-Dichotomy in the Palladium-Catalyzed Addition of Nucleophiles to Alkenes.
Chemistry - A European Journal. Roč. 21, č. 1 (2015), s. 36-56. ISSN 0947-6539. E-ISSN 1521-3765
Institucionální podpora: RVO:61388963
Klíčová slova: alkenes * catalysis * nucleophilic addition * palladium * stereochemistry
Kód oboru RIV: CC - Organická chemie
Impakt faktor: 5.771, rok: 2015
http://onlinelibrary.wiley.com/doi/10.1002/chem.201404070/pdf

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.
Trvalý link: http://hdl.handle.net/11104/0245924