14429-03-9Relevant articles and documents
Chiral cyclometalated iridium complexes for asymmetric reduction reactions
Smith, Jennifer,Kacmaz, Aysecik,Wang, Chao,Villa-Marcos, Barbara,Xiao, Jianliang
supporting information, p. 279 - 284 (2021/01/18)
A series of chiral cyclometalated iridium complexes have been synthesised by cyclometalating chiral 2-aryl-oxazoline and imidazoline ligands with [Cp?IrCl2]2. These iridacycles were studied for asymmetric transfer hydrogenation reactions with formic acid as the hydrogen source and were found to display various activities and enantioselectivities, with the most effective ones affording up to 63% ee in the asymmetric reductive amination of ketones and 77% ee in the reduction of pyridinium ions. This journal is
Protic additives or impurities promote imine reduction with pinacolborane
Huchenski, Blake S. N.,Speed, Alexander W. H.
supporting information, p. 1999 - 2004 (2019/02/20)
We report here that addition of stoichiometric amounts of alcohols or water to mixtures of imines and pinacolborane promote reduction reactions. The reactions of several imines were examined, revealing that alkyl imines were reduced, while aniline derived imines were not effectively reduced. The use of binol as an additive resulted in modest enantioinduction, however other chiral additives that were screened gave negligible enantioinduction. While the reactions described herein are not competitive in conversion with established imine reduction technologies, this work reveals that the presence of protic impurities must be considered as a promoter of side reactions in catalyzed imine hydroborations. Amines also promote imine reduction in certain cases, raising the possibility of a slow autocatalytic reaction. The ability of water or other protic impurities to promote the reduction of imines with pinacolborane represents an important identification of a potential source of background reaction in catalyzed reductions of imines.
Asymmetric Imine Hydroboration Catalyzed by Chiral Diazaphospholenes
Adams, Matt R.,Tien, Chieh-Hung,McDonald, Robert,Speed, Alexander W. H.
supporting information, p. 16660 - 16663 (2017/12/13)
The first use of diazaphospholenes as chiral catalysts has been demonstrated with enantioselective imine hydroboration. A chiral diazaphospholene prepared in a simple three-step synthesis from commercial materials has been shown to achieve the highest enantioselectivity for the hydroboration of alkyl imines with pinacolborane reported to date. Enantiomer ratios of up to 88:12 were obtained with low (2 mol %) catalyst loadings. Twenty examples of asymmetric reduction employing this main-group catalysis protocol, including the synthesis of the pharmaceuticals ent-rasagiline and fendiline, are shown.
