Issue 13, 2019

Selective reduction of formamides to O-silylated hemiaminals or methylamines with HSiMe2Ph catalyzed by iridium complexes

Abstract

The reaction of (4-methyl-pyridin-2-iloxy)ditertbutylsilane (NSitBu–H, 1) with [IrCl(coe)2]2 affords the iridium(III) complex [Ir(H)(Cl)(κ2-NSitBu)(coe)] (2), which has been fully characterized including X-ray diffraction studies. The reaction of 2 with AgCF3SO3 leads to the formation of species [Ir(H)(CF3SO3)(κ2-NSitBu)(coe)] (3). The iridium complexes 2 and 3 are effective catalysts for the reduction of formamides with HSiMe2Ph. The selectivity of the reduction process depends on the catalyst. Thus, by using complex 2, with a chloride ancillary ligand, it has been possible to selectively obtain the corresponding O-silylated hemiaminal by reaction of formamides with one equivalent of HSiMe2Ph, while complex 3, with a triflate ligand instead of chloride, catalyzed the selective reduction of formamides to the corresponding methylamine.

Graphical abstract: Selective reduction of formamides to O-silylated hemiaminals or methylamines with HSiMe2Ph catalyzed by iridium complexes

Supplementary files

Article information

Article type
Paper
Submitted
22 Dec. 2018
Accepted
25 Febr. 2019
First published
26 Febr. 2019

Dalton Trans., 2019,48, 4255-4262

Selective reduction of formamides to O-silylated hemiaminals or methylamines with HSiMe2Ph catalyzed by iridium complexes

J. Guzmán, A. M. Bernal, P. García-Orduña, F. J. Lahoz, L. A. Oro and F. J. Fernández-Alvarez, Dalton Trans., 2019, 48, 4255 DOI: 10.1039/C8DT05070H

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