Chelation-assisted carbonylation reactions catalyzed by Rh and Ru complexes
Chelation-assisted carbonylation reactions catalyzed by Rh and Ru complexes
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DOI：
10.1351/pac-con-09-10-15
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发表时间：
2010-07-01
影响因子：
1.8
通讯作者：
Fukumoto, Yoshiya
中科院分区：
文献类型：
--
作者：
Chatani, Naoto;Inoue, Satoshi;Fukumoto, Yoshiya
本文综述了后过渡金属催化的螯合辅助的羰基化反应。在吡啶-2-甲基甲醇和吡啶-2-甲胺存在下，这些催化剂实现了新的羰基化反应。反应涉及O-H和N-H键的活化，吡啶氮与Rh的配位是反应进行所必需的。此外，还证明了芳香酰胺中邻位C-H键的一种新的羰基化反应，其中的吡啶-2-甲基氨基部分起双齿导向基团的作用。在该反应中，从酰胺和Ru-3(CO)(12)的化学计量反应中分离到一个双核Ru配合物，其中酰胺以预期的N，N方式结合到一个Ru原子上，而羰基氧作为O-供体结合到另一个Ru原子上。这些研究表明，对于非螯合体系无法实现的新型羰化反应，络合方法学是有用的。
This account reviews chelation-assisted carbonylation reactions catalyzed by late transition metals. New carbonylation reactions are achieved with these catalysts in the presence of pyridin-2-ylmethanol and pyridin-2-ylmethylamine. The reactions involve activation of O-H and N-H bonds, coordination of the pyridine nitrogen to Rh being essential for the reaction to proceed. In addition, a new type of carbonylation of the ortho C-H bonds in aromatic amides in which the pyridin-2-ylmethylamino moiety functions as a bidentate directing group, is demonstrated. In this reaction, a dinuclear ruthenium complex was isolated from a stoichiometric reaction of amide and Ru-3(CO)(12), in which amide binds to one Ru atom in the expected N,N fashion and the carbonyl oxygen binds to the other Ru atom as an O-donor. These studies indicate that chelation methodology is useful for new types of carbonylation reaction, which cannot be achieved by non-chelation systems.