Cooperative dual catalysis: application to the highly enantioselective conjugate cyanation of unsaturated imides.
Cooperative dual catalysis: application to the highly enantioselective conjugate cyanation of unsaturated imides.
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DOI：
10.1021/ja046653n
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发表时间：
2004-07
影响因子：
15
通讯作者：
G. Sammis;H. Danjo;E. Jacobsen
中科院分区：
文献类型：
--
作者：
G. Sammis;H. Danjo;E. Jacobsen
采用协同异双金属催化作为设计原理，实现了氰化物与α，β-不饱和酰亚胺的对映选择性共轭加成的高反应性体系。涉及手性 (salen)Al 络合物 1b 和手性 (pybox)Er 络合物 4b 的双催化剂途径相对于单催化剂系统在速率和对映选择性方面提供了可测量的改进。机理研究指出了一种协同双金属机制，涉及 Al 络合物活化酰亚胺和 Er 络合物活化氰化物。
Cooperative heterobimetallic catalysis was used as a design principle to achieve a highly reactive system for the enantioselective conjugate addition of cyanide to alpha,beta-unsaturated imides. A dual-catalyst pathway involving chiral (salen)Al complex 1b and chiral (pybox)Er complex 4b provides measurable improvements in rates and enantioselectivities relative to single-catalyst systems. Mechanistic studies point to a cooperative bimetallic mechanism involving activation of the imide by the Al complex and activation of cyanide by the Er complex.