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  Polycationic Ligands in Gold Catalysis: Synthesis and Applications of Extremely π-Acidic Catalysts

Carreras, J., Gopakumar, G., Gu, L., Gimeno, A., Linowski, P., Petuškova, J., et al. (2013). Polycationic Ligands in Gold Catalysis: Synthesis and Applications of Extremely π-Acidic Catalysts. Journal of the American Chemical Society, 135(50), 18815-18823. doi:10.1021/ja411146x.

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Carreras, Javier1, Autor           
Gopakumar, Gopinadhanpillai2, Autor           
Gu, Lianghu1, Autor           
Gimeno, Ana1, Autor           
Linowski, Pawel1, Autor           
Petuškova, Jekaterina1, Autor           
Thiel, Walter2, Autor           
Alcarazo, Manuel1, Autor           
Affiliations:
1Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445592              
2Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              

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 Zusammenfassung: Very often ligands are anionic or neutral species. Cationic ones are rare, and, when used, the positively charged groups are normally appended to the periphery of the ligand. Here, we describe a dicationic phosphine with no spacer between the phosphorus atom and the two positively charged groups. This structural feature makes its donor ability poorer than that of phosphites and only comparable to extremely toxic or pyrophoric compounds such as PF3 or P(CF3)3. By exploiting these properties, a new Au catalyst has been developed displaying a dramatically enhanced capacity to activate π-systems. This has been used to synthesize very sterically hindered and naturally occurring 4,5-disubstituted phenanthrenes. The present approach is expected to be applicable to the development and improvement of many other transition metal catalyzed transformations that benefit from extremely strong π-acceptor ligands. The mechanism of selected catalytic transformations has been explored by density functional calculations.

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Sprache(n): eng - English
 Datum: 2013-07-092013-12-052013-12-18
 Publikationsstatus: Erschienen
 Seiten: 9
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1021/ja411146x
 Art des Abschluß: -

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Titel: Journal of the American Chemical Society
  Andere : J. Am. Chem. Soc.
  Kurztitel : JACS
Genre der Quelle: Zeitschrift
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Ort, Verlag, Ausgabe: American Chemical Society
Seiten: 9 Band / Heft: 135 (50) Artikelnummer: - Start- / Endseite: 18815 - 18823 Identifikator: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870