Amine Synthesis through Mild Catalytic Hydrosilylation of Imines using Polymethylhydroxysiloxane and [RuCl2(arene)]2 Catalysts
作者:Bin Li、Jean-Baptiste Sortais、Christophe Darcel、Pierre H. Dixneuf
DOI:10.1002/cssc.201100585
日期:2012.2.13
Tolerate silicone! The stable [RuCl2(p‐cymene]2 complex is an efficient catalyst for the direct chemoselective hydrosilylation of functionalized aldimines and ketimines into amines, usingpolymethylhydroxysiloxane as an inexpensive, stable, and safe hydrosilane source. The catalysis operates in ethanol, under air at room temperature, and tolerates the ketone ester and alkene functionality.
A Highly Efficient Base-Metal Catalyst: Chemoselective Reduction of Imines to Amines Using An Abnormal-NHC–Fe(0) Complex
作者:Mrinal Bhunia、Pradip Kumar Hota、Gonela Vijaykumar、Debashis Adhikari、Swadhin K. Mandal
DOI:10.1021/acs.organomet.6b00478
日期:2016.9.12
A base-metal, Fe(0)-catalyzed hydrosilylation of imines to obtain amines is reported here which outperforms its noble-metal congeners with the highest TON of 17000. The catalyst, (aNHC)Fe(CO)(4), works under very mild conditions, with extremely low catalyst loading (down to 0.005 mol %), and exhibits excellent chemoselectivity. The facile nature of the imine reduction under mild conditions has been further demonstrated by reducing imines towards expensive commercial amines and biologically important N-alkylated sugars, which are difficult to achieve otherwise. A mechanistic pathway and the source of chemoselectivity for imine hydrosilylation have been proposed on the basis of the well-defined catalyst and isolable intermediates along the catalytic cycle.