Introducing the Catalytic Amination of Silanes via Nitrene Insertion
| Autor: | Anabel M. Rodríguez, Jorge Pérez-Ruíz, Francisco Molina, Ana Poveda, Raúl Pérez-Soto, Feliu Maseras, M. Mar Díaz-Requejo, Pedro J. Pérez |
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| Rok vydání: | 2022 |
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| Zdroj: | Journal of the American Chemical Society. 144:10608-10614 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.2c03739 |
| Popis: | 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. We thank the Ministerio de Ciencia e Innovación for Grants PID2020-113797RB-C21, PID2020-112825RB-I00, and CEX2019-000925-S as well as FEDER for “Una manera de hacer Europa” funding. We also thank Junta de Andalucía (P20-00348) and Universidad de Huelva (P.O.Feder UHU202016). A.M.R. and R.P.-S. thank Ministerio de Universidades for the FPU fellowships (FPU17/02738 and FPU18/ 01138, respectively), and J.P.-R. thanks Fondo de Garantía Juvenil for a research contract. CERCA Programme/Generalitat de Catalunya is also acknowledged. We thank Prof. T. R. Belderrain for helpful discussions on 29Si NMR spectroscopy. Funding for open access charge: Universidad de Huelva / CBUA |
| Databáze: | OpenAIRE |
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