Asymmetric Hydrogenation of Trisubstituted Olefins with Iridium−Phosphine Thiazole Complexes: A Further Investigation of the Ligand Structure

作者：Christian Hedberg, Klas Källström, Peter Brandt, Lars Kristian Hansen, Pher G. Andersson · 发表于：Journal of the American Chemical Society · 年份：2006 · DOI：10.1021/ja057178b · 被引用次数：158 · 研究领域：Asymmetric Hydrogenation and Catalysis、Advanced Synthetic Organic Chemistry、Carbon dioxide utilization in catalysis

New chiral bidentate phoshine thiazoles have been prepared and successfully applied as ligands in the homogeneous iridium-catalyzed asymmetric hydrogenation of aryl alkenes and aryl alkene esters. The ligands are designed to be highly modular and have one common chiral intermediate, from which diversity can be introduced at a late stage in the synthetic pathway. It was found that a six-member-ring backbone of the rigid ligand structure was preferred over seven- or five-member rings. In this study it is shown that the substituent pattern of the ligands has a major influence on the stereochemical outcome of the products. By applying the selectivity model proposed in this study, it is possible to match different substrates against different catalysts. In this way, good to excellent enantioselectivity can be obtained for typically difficult substrates. Geometrically different derivatives of alpha- and beta-methyl cinnamic acid ethyl esters were hydrogenated, to demonstrate the validity of the selectivity model and to verify the importance of steric and electronic matching of the catalyst and the substrate.