CD2Cl2) and on the concentration. Complexes 3a,b catalyze the decomposition of ethyl diazoacetate to give, in the presence of styrene, the corresponding cyclopropanation products with enantioselectivity up to 35% ee and E/Z ratios of about 55:45. Complexes 3a,b also catalyze the epoxidation of unfunctionalized olefins with iodosyl benzene as the primary oxidant. High olefin conversions and fair selectivity
六配位配合物反式-[RuCl 2(PP *)2 ](PP * =(S,S)-1,2-双(1-
萘基
苯基膦基)
乙烷(bnpe),2a ;(S,已经制备了S)-2,3-双(
二苯基膦基)
丁烷(chiraphos)2b)并对其结构进行了表征。对2a和b的X射线研究表明,在高度拥挤的八面体环境中,PPh 2基团的取代基具有非C 2对称构象。络合物2a,b在CH 2 Cl 2中与Tl [PF 6 ]反应得到相应的一
氯阳离子衍
生物[RuCl(P * P *)2 ] PF 6(PP * = bnpe,3a ; chiraphos,3b)。bnpe衍
生物3a在固态(通过X射线研究)和溶液(通过31 P NMR光谱)中均为五坐标。Chiraphos类似物3b在溶液中明显二聚,这取决于溶剂(CDCl 3或CD 2 Cl 2)和浓度。配合物3a,b在
苯乙烯存在下,催化
重氮乙酸乙酯的分解得到相应的
环丙烷化产物,其对映选择性高达35%ee,E