Introducing the Catalytic Amination of Silanes via Nitrene Insertion
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Author
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Publication Date
2022-06-01 -
Publisher
American Chemical Society -
Citation
Rodríguez, A. M., Pérez-Ruíz, J., Molina, F., Poveda, A., Pérez-Soto, R., Maseras, F., Díaz-Requejo, M. M., & Pérez, P. J. (2022). Introducing the Catalytic Amination of Silanes via Nitrene Insertion. In Journal of the American Chemical Society (Vol. 144, Issue 23, pp. 10608–10614). American Chemical Society (ACS). https://doi.org/10.1021/jacs.2c03739 -
Abstract
The direct functionalization of Si−H bonds by the nitrene insertion methodology is described. A copper(I) complex bearing a trispyrazolylborate ligand catalyzes the transfer of a nitrene group from PhINTs to the Si−H bond of silanes, disilanes, and siloxanes, leading to the exclusive formation of Si−NH moieties in the first example of this transformation. The process tolerates other functionalities in the substrate such as several C−H bonds and alkyne and alkene moieties directly bonded to the silicon center. Density functional theory (DFT) calculations provide a mechanistic interpretation consisting of a Si−H homolytic cleavage and subsequent rebound to the Si-centered radical.
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jacs.2c03739.pdf | 3.076Mb | View/ | Versión editor |
Fichero | Tamaño | Formato |
| Description |
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jacs.2c03739.pdf | 3.076Mb | View/ | Versión editor |