Efficient preparation of new rhodium- and iridium-[bis(oxazolinyl)-3,5-dimethylphenyl] complexes by C-H bond activation: Applications in asymmetric synthesis

Efficient preparation of new rhodium- and iridium-[bis(oxazolinyl)-3,5-dimethylphenyl] complexes by C-H bond activation: Applications in asymmetric synthesis
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DOI:
10.1002/adsc.200606049
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发表时间:
2006-07-01
影响因子:
5.4
通讯作者:
Nishiyama, Hisao
Nishiyama, Hisao
中科院分区:
化学2区
文献类型:
--
作者:
Ito, Jun-ichi;Shiomi, Takushi;Nishiyama, Hisao

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以4,6-二甲基-1,3-双(恶唑啉)苯衍生物为原料,采用C-H键活化法合成了双(恶唑啉)-3,5-二甲基苯基铑、铱配合物。考察了配合物对(E)-乙基3-苯基丁-2-烯酸酯的不对称共轭还原反应和丙烯酸叔丁酯与苯甲醛的不对称还原Aldol反应的催化活性。结果表明,3,5-dmPhebox的铑配合物具有较高的催化活性,而相应的铱配合物的催化活性较低。
The bis(oxazolinyl)-3,5-dimethylphenylrhodium and -iridium complexes were synthesized in high yields by an efficient C-H bond activation method with 4,6-dimethyl-1,3-bis(oxazolinyl)benzene derivatives. The catalytic activity of the complexes was examined for the asymmetric conjugate reduction of (E)-ethyl 3-phenylbut-2-enoate and the asymmetric reductive aldol reaction of tert-butyl acrylate and benzaldehyde. It was found that the rhodium complex of 3,5-dmPhebox showed the higher catalytic activity, whereas the corresponding iridium complexes proved to be less active.