Isomerization of terminal epoxides by a [Pd-H] catalyst: a combined experimental and theoretical mechanistic study.
Isomerization of terminal epoxides by a [Pd-H] catalyst: a combined experimental and theoretical mechanistic study.
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DOI：
10.1021/ja400325w
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发表时间：
2013-04
影响因子：
15
通讯作者：
Devendra J. Vyas;E. Larionov;C. Besnard;L. Guénée;C. Mazet
中科院分区：
文献类型：
--
作者：
Devendra J. Vyas;E. Larionov;C. Besnard;L. Guénée;C. Mazet
一种不寻常的钯氢化物络合物已被证明是一个称职的催化剂在异构化的各种终端和内部的环氧化物。该反应具有广泛的应用范围和合成实用性。实验和理论证据提供了一个前所未有的氢化物机制，其特征在于由两个不同的对映体确定步骤。这些结果为发展该反应的对映选择性变体提供了希望。
An unusual palladium hydride complex has been shown to be a competent catalyst in the isomerization of a variety of terminal and internal epoxides. The reaction displayed broad scope and synthetic utility. Experimental and theoretical evidence are provided for an unprecedented hydride mechanism characterized by two distinct enantio-determining steps. These results hold promise for the development of an enantioselective variant of the reaction.