A New and Highly Efficient Asymmetric Route to Cyclic α-Amino Phosphonates: The First Catalytic Enantioselective Hydrophosphonylation of Cyclic Imines Catalyzed by Chiral Heterobimetallic Lanthanoid Complexes
A New and Highly Efficient Asymmetric Route to Cyclic α-Amino Phosphonates: The First Catalytic Enantioselective Hydrophosphonylation of Cyclic Imines Catalyzed by Chiral Heterobimetallic Lanthanoid Complexes
复制标题
DOI：
10.1021/ja973872i
复制
发表时间：
1998-03
影响因子：
15
通讯作者：
H. Gröger;Yoshinobu Saida;H. Sasai;K. Yamaguchi;J. Martens;M. Shibasaki
中科院分区：
文献类型：
--
作者：
H. Gröger;Yoshinobu Saida;H. Sasai;K. Yamaguchi;J. Martens;M. Shibasaki
首次描述了环状亚胺的催化和对映选择性氢膦酰化。此外，我们还发现了一种使用噻唑啉作为亚胺模型组分制备环状 α-氨基膦酸酯的新型高效不对称方法。所需的药学上感兴趣的膦酸酯 5a−e 可以通过 CN 双键的异双金属 (R)-LnPB 催化（Ln = 镧系金属，P = 钾，B = (R)=联萘酚）氢膦酰化来合成，对映体过量高达 98%，化学产率高达 98%。使用其他类型的有机金属催化剂（钛（IV）络合物），反应以适度的对映选择性进行。报告了对映选择性和化学产率分别与一系列反应参数（例如，镧系元素和碱金属、溶剂、反应温度、压力和催化量）的依赖性的详细研究。优化的催化镧系元素系统“(R)-YbPB (5 mol %)/50 °C/48 h/THF−甲苯 (1:7)...
The catalytic and enantioselective hydrophosphonylation of cyclic imines is described for the first time. In addition, we have uncovered a new and highly efficient asymmetric approach to cyclic α-amino phosphonates using thiazolines as the imine model component. The desired pharmaceutically interesting phosphonates 5a−e could be synthesized by a heterobimetallic (R)-LnPB-catalyzed (Ln = lanthanoid metal, P = potassium, B = (R)=binaphthol) hydrophosphonylation of the CN double bond with up to 98% enantiomeric excess and up to 98% chemical yield. Using other types of organometallic catalysts (titanium(IV) complexes), the reaction proceeds with modest enantioselectivity. A detailed investigation concerning the dependence of enantioselectivity and chemical yield, respectively, on a series of reaction parameters (e.g., lanthanoid and alkali metal, solvent, reaction temperature, pressure, and catalytic amount) is reported. An optimized catalytic lanthanoid system “(R)-YbPB (5 mol %)/50 °C/48 h/THF−toluene (1:7)...