• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Chemistry: A European journal >Bulky phosphinines: From a molecular design to an application in homogeneous catalysis
【24h】

Bulky phosphinines: From a molecular design to an application in homogeneous catalysis

机译：庞大的膦亚胺：从分子设计到均相催化的应用

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The design and preparation of an asymmetrically substituted and bulky phosphinine was achieved by introducing sterically demanding substituents into specific positions of a rigid phosphorus-heterocyclic framework. Compound 5 shows, at the same time, axial chirality and a sufficiently high energy barrier for internal rotation to prevent enantiomerization. Both enantiomers of 5 were isolated by means of chiral analytical HPLC, and their absolute configurations could be assigned by combining experimental data and DFT calculations. Despite its substitution pattern, 5 can still coordinate to transition-metal centers through the lone pair of electrons on the phosphorus atom. Rapid C-H activation on the adjacent aryl substituent at the 2-position of the phosphorus heterocycle was achieved by using [{CpIrCl_2}_2] (Cp=1,2,3,4,5- pentamethylcyclopentadienyl) as a metal precursor. A racemic mixture of 5 was applied as a π-accepting low-coordinate phosphorus ligand in the Rh-catalyzed hydroformylation of trans-2-octene, which showed a clear preference for the formation of 2-methyloctanal. Bulky phosphinines: An asymmetrically substituted, bulky, and atropisomeric phosphinine has been prepared and characterized (see figure). Rapid C-H activation on the 2-aryl substituent of the phosphorus heterocycle was achieved with [{CpIrCl_2}_2] (Cp=1,2,3,4,5-pentamethylcyclopentadienyl) as a metal precursor. A racemic mixture of the phosphinine acted as a π-accepting low-coordinate phosphorus ligand in the Rh-catalyzed hydroformylation of 2-octene.
机译：通过将空间上需要的取代基引入到刚性的磷-杂环骨架的特定位置，可以实现不对称取代的大体积次膦的设计和制备。化合物5同时显示出轴向手性和足够高的能垒，以用于内部旋转以防止对映异构化。通过手性分析HPLC分离5种对映体，可以通过结合实验数据和DFT计算来确定其绝对构型。尽管有其取代模式，但5仍可以通过磷原子上孤对的电子与过渡金属中心配位。通过使用[{CpIrCl_2} _2]（Cp = 1,2,3,4,5-五甲基环戊二烯基）作为金属前体，可以在磷杂环2位附近的相邻芳基取代基上实现快速C-H活化。 5的外消旋混合物被用作反式-2-辛烯的Rh催化加氢甲酰化反应中的一种π受体低配位磷配体，这显然表明其倾向于形成2-甲基辛醛。庞大的膦亚胺：已制备并表征了不对称取代的，庞大的和阻转异构的次膦（见图）。用[{CpIrCl_2} _2]（Cp = 1,2,3,4,5-五甲基环戊二烯基）作为金属前体，可在磷杂环基的2-芳基取代基上实现快速C-H活化。膦的外消旋混合物在Rh催化的2-辛烯加氢甲酰化反应中充当π接受的低配位磷配体。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号