Details
| Titel in Übersetzung | Oxidative aromatische Kupplung und Scholl-Reaktion im Vergleich |
|---|---|
| Originalsprache | Englisch |
| Seiten (von - bis) | 9900-9930 |
| Seitenumfang | 31 |
| Fachzeitschrift | Angewandte Chemie |
| Jahrgang | 52 |
| Ausgabenummer | 38 |
| Publikationsstatus | Veröffentlicht - 14 Juli 2013 |
Abstract
Does the dehydrogenative coupling of aromatic compounds mediated by AlCl3 at high temperatures and also by FeCl3, MoCl 5, PIFA, or K3[Fe(CN)6] at room temperature proceed by the same mechanism in all cases? With the growing importance of the synthesis of aromatic compounds by double CH activation to give various biaryl structures, this question becomes pressing. Since some of these reactions proceed only in the presence of non-oxidizing Lewis acids and some only in the presence of certain oxidants, the authors venture the hypothesis that, depending on the electronic structure of the substrates and the nature of the "catalyst", two different mechanisms can operate. One involves the intermediacy of a radical cation and the other the formation of a sigma complex between the acid and the substrate. The goal of this Review is to encourage further mechanistic studies hopefully leading to an in-depth understanding of this phenomenon. Where is the oxidant? Although the coupling of arenes in the presence of Lewis acids has been known for some time, the differentiation between reactions in the presence of a non-oxidizing Lewis acid (Scholl reaction) and in the presence of an oxidizing Lewis acid has been lost over the years. This Review highlights the similarities and differences between these reactions, which most probably proceed by two different mechanisms.
ASJC Scopus Sachgebiete
- Chemische Verfahrenstechnik (insg.)
- Katalyse
- Chemie (insg.)
- Allgemeine Chemie
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in: Angewandte Chemie , Jahrgang 52, Nr. 38, 14.07.2013, S. 9900-9930.
Publikation: Beitrag in Fachzeitschrift › Übersichtsarbeit › Forschung › Peer-Review
}
TY - JOUR
T1 - Comparison of oxidative aromatic coupling and the scholl reaction
AU - Grzybowski, Marek
AU - Skonieczny, Kamil
AU - Butenschön, Holger
AU - Gryko, Daniel T.
PY - 2013/7/14
Y1 - 2013/7/14
N2 - Does the dehydrogenative coupling of aromatic compounds mediated by AlCl3 at high temperatures and also by FeCl3, MoCl 5, PIFA, or K3[Fe(CN)6] at room temperature proceed by the same mechanism in all cases? With the growing importance of the synthesis of aromatic compounds by double CH activation to give various biaryl structures, this question becomes pressing. Since some of these reactions proceed only in the presence of non-oxidizing Lewis acids and some only in the presence of certain oxidants, the authors venture the hypothesis that, depending on the electronic structure of the substrates and the nature of the "catalyst", two different mechanisms can operate. One involves the intermediacy of a radical cation and the other the formation of a sigma complex between the acid and the substrate. The goal of this Review is to encourage further mechanistic studies hopefully leading to an in-depth understanding of this phenomenon. Where is the oxidant? Although the coupling of arenes in the presence of Lewis acids has been known for some time, the differentiation between reactions in the presence of a non-oxidizing Lewis acid (Scholl reaction) and in the presence of an oxidizing Lewis acid has been lost over the years. This Review highlights the similarities and differences between these reactions, which most probably proceed by two different mechanisms.
AB - Does the dehydrogenative coupling of aromatic compounds mediated by AlCl3 at high temperatures and also by FeCl3, MoCl 5, PIFA, or K3[Fe(CN)6] at room temperature proceed by the same mechanism in all cases? With the growing importance of the synthesis of aromatic compounds by double CH activation to give various biaryl structures, this question becomes pressing. Since some of these reactions proceed only in the presence of non-oxidizing Lewis acids and some only in the presence of certain oxidants, the authors venture the hypothesis that, depending on the electronic structure of the substrates and the nature of the "catalyst", two different mechanisms can operate. One involves the intermediacy of a radical cation and the other the formation of a sigma complex between the acid and the substrate. The goal of this Review is to encourage further mechanistic studies hopefully leading to an in-depth understanding of this phenomenon. Where is the oxidant? Although the coupling of arenes in the presence of Lewis acids has been known for some time, the differentiation between reactions in the presence of a non-oxidizing Lewis acid (Scholl reaction) and in the presence of an oxidizing Lewis acid has been lost over the years. This Review highlights the similarities and differences between these reactions, which most probably proceed by two different mechanisms.
KW - arene coupling
KW - biaryls
KW - Lewis acids
KW - oxidative coupling
KW - Scholl reaction
UR - http://www.scopus.com/inward/record.url?scp=84884283349&partnerID=8YFLogxK
U2 - 10.1002/anie.201210238
DO - 10.1002/anie.201210238
M3 - Review article
AN - SCOPUS:84884283349
VL - 52
SP - 9900
EP - 9930
JO - Angewandte Chemie
JF - Angewandte Chemie
SN - 1433-7851
IS - 38
ER -