Enantioselective Catalysis, XV Preparative and Structural Chemistry of Diastereomeric Derivatives of 3‐Phosphanylpyrrolidine and Their Palladium(II) Complexes ‐ Asymmetric Grignard Cross‐Coupling Reaction
作者:Ulrich Nagel、Hans Günter Nedden
DOI:10.1002/cber.19971300729
日期:1997.7
3-(phosphanyl) pyrrolidine part of these ligands. Optimisation of enantioselectivity with these ligands can be carried out by a variation of the ligand to nickel ratio and by the choice of the vinyl halide used as starting compound. The catalytic cycle must contain at least one catalytically active species, bearing more than one β aminoalkylphosphane ligand.
制备3-(二苯基膦基)吡咯烷具有手性(四氢呋喃-2-基)甲基和[(N-新戊基)吡咯烷二-2-基]甲基作为吡咯烷氮原子上的取代基的非对映异构衍生物和(2 S据报道有,4 S)-1-苄基-4-(二苯基膦基)-2-(甲氧基甲基)吡咯烷。[3 S,P(RS)]-3-(苯基膦烷基)吡咯烷在磷上带有一个额外的手性中心,是制备膦的起始原料,其中PPh 2部分的一个苯基被2取代。 -甲氧基苯基(= An)或2,4,6-三甲氧基苯基(= TMP)。PdI 2这些配体的配合物通过硅胶柱色谱分离成非对映异构体。通过X射线晶体学和NMR研究了这些新型膦非对映异构体及其PdI 2配合物的结构化学。在P,N仅对P,N,N'配位体发现碘化物阴离子的钯配位中心位移。在镍络合物催化的交叉偶联反应中,生成3-苯基-1-丁烯,在简单的1-烷基-3-(二苯基膦基)吡咯烷配体的情况下,我们获得了最高的对映选择性。用带有另外的醚或胺