摘要
从天然樟脑的衍生物出发,用二异丙氨基溴化镁作为缩合剂,在温和的条件下合成了手性配体d,d-二龙脑酰基甲烷,然后将其与FeCl3络合,首次制备了(d,d-二龙脑酰基甲烷)铁(Ⅲ)配合物.通过1HNMR,IR和元素分析对配合物的结构进行了表征,并用它来催化苯乙烯在空气作用下的不对称环氧化反应,主要得到了S-苯基环氧乙烷.考察了不同结构的醛、空气流量、催化剂用量和反应温度等因素对苯乙烯环氧化反应产物收率和光学ee值的影响.结果表明,当醛为2-乙基丁醛,空气流量为12ml/min,催化剂用量为2%和反应温度为30℃时,苯基环氧乙烷的收率和ee值最高,分别为89.7%和78.1%.
A chiral β-diketone d,d-dicampholylmethanato (Hdcm) was synthesized in high yield from natural d-camphor ramifications by using magnesium bromide diisopropylamide under mild conditions. A new chiral complex tris(d,d-dicampholylmethanato)iron(Ⅲ) (Fe(dcm)_3) was obtained from Hdcm and FeCl_3, and characterized by 1H NMR, IR and elemental analysis. The complex catalyzed the asymmetric epoxidation of styrene, and S-styrene oxide was obtained mainly. The effect of aldehyde structure, air flow rate, catalyst amount and reaction temperature on the product yield and enantioselectivity was investigated. The result showed that when the epoxidation was carried out with a catalyst amount of 2%, air flow rate of 12 ml/min and 2-ethylbutyraldehyde as sacrificial aldehyde at 30 ℃, the yield and enantiomeric excess of S-styrene oxide reached 89.7% and 78.1%, respectively.
出处
《催化学报》
SCIE
CAS
CSCD
北大核心
2005年第4期291-295,共5页
基金
教育部高等学校骨干教师资助计划项目(200065)
