Chemoselective Reduction of Imines Catalyzed by Ruthenium(II) Half‐Sandwich Complexes: A Mechanistic Study

Abstract

Ruthenium half‐sandwich complexes ligated to chiral 2‐oxazolidinethiones or 2‐thiozolidinethiones in the reduction of N‐benzylideneaniline using silyl hydrides as reductants has been examined. The chemoselective reduction of imines takes place under mild conditions to afford the corresponding amines in nearly quantitative yield. Mechanistic studies indicate that dissociation of the ancillary ligands generate the active catalyst in all the complexes studied, which is the same species generated by [Ru(p‐cymene)(Cl)2]2 under the reaction conditions. This results in the formation of a single catalytic species irrespective of the starting half‐sandwich complex. Detailed mechanistic studies involving trapping of intermediates, in situ studies using mass spectrometry and NMR spectroscopy were carried out using the active catalyst generated by [Ru(p‐cymene)(Cl)2]2. The mechanism of the reaction is dependent on the number of the hydrogen atoms in the reducing silane. The reaction proceeds via Gade‐Hoffman pathway or Zheng‐Chan pathway when a dihydro or trihydrosilane is the reductant. However, the use of a monohydrosilane, leads to longer reaction times presumably due to a change in the reaction pathway.

Cathode enabled high faradaic efficiency: reduction of imines to amines with H2O as a H-source

“…5 A straightforward route toward its construction might be the reduction of imines that are readily prepared from commercially available aldehydes and primary amines. However, limited by the atom uneconomical H-source (metal hydride reagents, 6 hydrosilanes 7 ) or the transition metal (Pd, 8 Mo/W, 9 Rh, 10 Ru 11 and Ir 12 ) catalysts, this common strategy suffers from some difficulties to achieve wide adoption (Scheme 1b). Therefore, it is highly demanded to develop a versatile and green protocol for efficiency to be obtained (Scheme 1c).…”