| 链接基团对固载手性Salen Mn(Ⅲ)催化不对称环氧化反应的影响 | |
| Effect of Axial Linker Group on Heterogeneous Chiral Salen Mn(Ⅲ) Catalyzed Enantioselective Epoxidation of Unfunctionalized Olefins | |
| 摘要: 制备了二胺和二酚修饰的晶态有机聚合物-无机杂化载体低聚苯乙烯基膦酸-膦酸氢锆(LCZSPP)轴向固载手性Salen Mn(Ⅲ)催化剂，将其应用于非官能烯烃的多相不对称环氧化反应。研究了两类轴向连接基团及助催化剂在催化不对称环氧化反应中的影响。结果表明，通过二胺为链接基团固载的催化剂在加入轴向助剂(NMO)的情况下，转化率和对映选择性都有较大提高。然而，与文献报道相反，二酚固载的催化剂在不添加轴向助剂的情况下，转化率和对映选择性都比添加轴向助剂有明显提高。此外，制备的固载催化剂可以很容易从反应体系中分离出来，并且在重复使用10次以上后，催化活性和对映选择性都没有明显的降低。 | |
| 关键词: 低聚苯乙烯基膦酸-膦酸氢锆 手性Salen Mn(Ⅲ) 多相催化剂 非官能化烯烃的不对称环氧化反应 轴向助催化剂 | |
| 基金项目: | |
| Abstract: The chiral Salen Mn(Ⅲ) was axially immobilized onto a diamine or diphenoxyl linker modified layered crystalline hybrid material-zirconium oligostyrenylphosphonate-phosphate (LCZSPP) synthesized in this lab. The influence of the two types of linkers and axial additives on the catalytic performance of the heterogeneous Salen Mn(Ⅲ) was investigated. The results demonstrate that the conversion and enantioselectivity(ee) value increase in the presence of axial additive such as NMO for the Salen Mn(Ⅲ) immobilized onto LCZSPP via diamine linkers while the opposite is true for the immobilized Salen Mn(Ⅲ) via diphenoxyl. In addition, the prepared catalysts could be conveniently separated from the reaction system by simple precipitation in hexane, and could be reused at least ten times without significant loss of activity and enantioselectivity. | |
| Keywords: zirconium oligostyrenylphosphonate-phosphate chiral Salen Mn(Ⅲ) heterogeneous catalysts enantioselective epoxidation of unfunctionalized olefins axial additive | |
| 摘要点击次数: 1655 | |
| 全文下载次数: 1920 | |
| 罗云飞,傅相锴,邹晓川,王长炜,胡小艳,贾紫永,张怀志.链接基团对固载手性Salen Mn(Ⅲ)催化不对称环氧化反应的影响[J].无机化学学报,2011,27(7):1302-1308. | |
| 查看全文 查看/发表评论 下载PDF阅读器 | |
| Support information: | |
|
| |
|
| |
|
| |