Synthesis and reactions of phosphine-boranes. Synthesis of new bidentate ligands with homochiral phosphine centers via optically pure phosphine-boranes
Synthesis and reactions of phosphine-boranes. Synthesis of new bidentate ligands with homochiral phosphine centers via optically pure phosphine-boranes
Iridium Complexes with Phosphine−Phosphite Ligands. Structural Aspects and Application in the Catalytic Asymmetric Hydrogenation of N-Aryl Imines
作者:Sergio Vargas、Miguel Rubio、Andrés Suárez、Diego del Río、Eleuterio Álvarez、Antonio Pizzano
DOI:10.1021/om050885t
日期:2006.2.1
A family of modularly designed phosphine-phosphites (P-OP), possessing a C-C-O backbone, has been synthesized and evaluated in the iridium-catalyzed asymmetric hydrogenation of N-aryl imines. The enantioselectivity of this reaction is highly dependent on the nature of the ligand, and catalysts bridged by an oxyethylene fragment have produced significantly higher enantiomeric excesses (Delta ee > 20%) than their o-oxyphenylene counterparts. Structural studies by X-ray crystallography and NMR spectroscopy of complexes with the formulation [Ir(COD)(P-OP)]BF4 and Ir(Cl)(CO)(P-OP), complemented by DFT calculations of model compounds of the chlorocarbonyls, have shown important differences between complexes bridged by an aliphatic or an aromatic bridge, regarding the iridacycle conformation and the location of phosphine substiments. Catalyst optimization has afforded enantioselectivities from 72 to 85% ee in the hydrogenation of several N-aryl imines.
Synthesis and reactions of phosphine-boranes. Synthesis of new bidentate ligands with homochiral phosphine centers via optically pure phosphine-boranes
作者:Tsuneo Imamoto、Toshiyuki Oshiki、Takashi Onozawa、Tetsuo Kusumoto、Kazuhiko Sato