RT Journal Article
T1 Introducing the Catalytic Amination of Silanes via Nitrene Insertion
A1 Moreno Rodríguez, Anabel
A1 Pérez Ruíz, Jorge
A1 Molina González, Francisco
A1 Poveda, Ana
A1 Pérez Soto, Raúl
A1 Maseras, Feliu
A1 Díaz Requejo, María Mar
A1 Pérez Romero, Pedro José
AB 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 PhINTs 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.
PB American Chemical Society
SN 1520-5126 (electrónico)
SN 0002-7863
YR 2022
FD 2022-06-01
LK https://hdl.handle.net/10272/21350
UL https://hdl.handle.net/10272/21350
LA eng
NO 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
NO 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
DS Repositorio Institucional de la Universidad de Huelva
RD 31 may 2026