| Online-Ressource |
Verfasst von: | Jin, Hongming [VerfasserIn]  |
| Tong, Wen-Yan [VerfasserIn]  |
| Zhang, Jing [VerfasserIn]  |
| Rudolph, Matthias [VerfasserIn]  |
| Rominger, Frank [VerfasserIn]  |
| Shen, Xu [VerfasserIn]  |
| Qu, Shuanglin [VerfasserIn]  |
| Hashmi, A. Stephen K. [VerfasserIn]  |
Titel: | Dichotomy of platinum(II) and gold(III) carbene intermediates switching from N- to O-selectivity |
Verf.angabe: | Hongming Jin, Wen-Yan Tong, Jing Zhang, Matthias Rudolph, Frank Rominger, Xu Shen, Shuanglin Qu & A. Stephen K. Hashmi |
E-Jahr: | 2022 |
Jahr: | 30 March 2022 |
Umfang: | 11 S. |
Fussnoten: | Im Text sind "N" und "O" kursiv geschrieben ; Gesehen am 04.06.2022 |
Titel Quelle: | Enthalten in: Nature Communications |
Ort Quelle: | [London] : Nature Publishing Group UK, 2010 |
Jahr Quelle: | 2022 |
Band/Heft Quelle: | 13(2022), Artikel-ID 1672, Seite 1-11 |
ISSN Quelle: | 2041-1723 |
Abstract: | Pt(II) and Au(III)-mediated intermolecular divergent annulations of benzofurazans and ynamides highlighted the N- to O-selectivity of tunable metal carbene intermediates. PtCl2 with a bulky phosphite ligand resulted in the specific synthesis of six-membered quinoxaline N-oxides and successfully suppressed the in-situ deoxygenation of N-oxides. On the other hand, an unique gold(III) catalyst (2,6-di-MeO-PyrAuCl3) led to the five-membered ring products, benzimidazoles. A broad scope of functional groups was well compatible, delivering better yields and selectivities in contrast to conventional gold(I) catalysts. The different behavior of presumed platinum(II) and gold(III) carbenes with respect to chemoselectivity was intensively examined by experiments and DFT calculations. A detailed mechanistic study, based on DFT calculations, revealed that the highly electrophilic carbocation-like gold(III) carbene triggers an oxophilic cyclization, followed by a cascade ring contraction and acyl migration. On the contrary, the Pt carbene species is less cationic, favoring the formation of the six-membered ring via N-attack. |
DOI: | doi:10.1038/s41467-022-29326-0 |
URL: | Bitte beachten Sie: Dies ist ein Bibliographieeintrag. Ein Volltextzugriff für Mitglieder der Universität besteht hier nur, falls für die entsprechende Zeitschrift/den entsprechenden Sammelband ein Abonnement besteht oder es sich um einen OpenAccess-Titel handelt.
Volltext ; Verlag: https://doi.org/10.1038/s41467-022-29326-0 |
| Volltext: https://www.nature.com/articles/s41467-022-29326-0 |
| DOI: https://doi.org/10.1038/s41467-022-29326-0 |
Datenträger: | Online-Ressource |
Sprache: | eng |
Sach-SW: | Homogeneous catalysis |
| Reaction mechanisms |
K10plus-PPN: | 1806075997 |
Verknüpfungen: | → Zeitschrift |
Dichotomy of platinum(II) and gold(III) carbene intermediates switching from N- to O-selectivity / Jin, Hongming [VerfasserIn]; 30 March 2022 (Online-Ressource)