Selective Hydrogenation of α,β-Unsaturated Aldehydes and Ketones by Air-Stable Ruthenium NNS Complexes
作者:Pim Puylaert、Richard van Heck、Yuting Fan、Anke Spannenberg、Wolfgang Baumann、Matthias Beller、Jonathan Medlock、Werner Bonrath、Laurent Lefort、Sandra Hinze、Johannes G. de Vries
DOI:10.1002/chem.201700806
日期:2017.6.22
The selective hydrogenation of the carbonyl functionality of α,β-unsaturated aldehydes and ketones is catalysed by ruthenium dichloride complexes bearing a tridentate NNS ligand as well as triphenylphosphine. The tridentate ligand backbone is flexible, as evidenced by the equilibrium observed in solution between the cis- and trans-isomers of the dichloride precatalysts, as well as crystal structures
α,β-不饱和醛和酮的羰基官能团的选择性氢化是通过带有三齿NNS配体以及三苯基膦的二氯化钌配合物催化的。三齿配体主链是柔性的,如顺式和反式之间在溶液中观察到的平衡所证明的那样。二氯化物预催化剂的α-异构体,以及其中一些配合物的晶体结构。该复合物在氢存在下被碱活化,并在温和条件下易于氢化羰基官能团。尽管通过碱进行了活化,但是由于碱的含量低,即使对于醛底物,副反应也可以忽略不计。因此,可以在10–25 mmol范围内以很高的收率分离出相应的烯丙醇。营业额达到20万。