Chiral phosphine-olefin ligands in the rhodium-catalyzed asymmetric 1,4-addition reactions
Chiral phosphine-olefin ligands in the rhodium-catalyzed asymmetric 1,4-addition reactions
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DOI：
10.1021/ja0671013
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发表时间：
2007-02-21
影响因子：
15
通讯作者：
Hayashi, Tamio
中科院分区：
文献类型：
--
作者：
Duan, Wei-Liang;Iwamura, Hiroshi;Hayashi, Tamio
综述了手性膦-烯烃配体1在铑催化的芳基硼酸与α，β-不饱和羰基化合物的不对称1，4-加成反应中的应用。通过比较实验结果和X-射线晶体结构，证明Rh/1配合物的有效手性环境与Rh/（R，R）-Ph-bod* 配合物的有效手性环境相似。高催化活性的Rh/1配合物被公开，并通过使用反应量热计和P-31 NMR光谱的机理研究建立了涉及三聚体-单体平衡的催化循环。还成功地观察到来自催化剂的非活性三聚体-活性单体平衡的负非线性效应。
A full overview on the use of chiral phosphine-olefin ligands 1 in the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyl compounds is described. Effective chiral environment of a Rh/1 complex was shown to resemble that of a Rh/(R,R)-Ph-bod* complex by comparing the experimental results as well as the X-ray crystal structures. High catalytic activity of a Rh/1 complex was disclosed and the catalytic cycle involving a trimer-monomer equilibrium was established through mechanistic studies using a reaction calorimeter and P-31 NMR spectroscopy. A negative nonlinear effect derived from an inactive trimer-active monomer equilibrium of the catalyst was also successfully observed.