Synthesis of enantiomerically pure P-stereogenic diphosphacrowns and their palladium complexes.
Synthesis of enantiomerically pure P-stereogenic diphosphacrowns and their palladium complexes.
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DOI：
10.1021/jo1024442
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发表时间：
2011-02
期刊：
影响因子：
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通讯作者：
Y. Morisaki;Hiroaki Imoto;K. Hirano;Tamio Hayashi;Y. Chujo
中科院分区：
文献类型：
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作者：
Y. Morisaki;Hiroaki Imoto;K. Hirano;Tamio Hayashi;Y. Chujo
以P-立体双膦作为手性构筑块，开发了一条合成对映体纯的P-立体双膦冠醚的实用路线。其分子结构经核磁共振谱和X射线结晶学确证。将双膦冠醚与钯进行络合反应，得到了相应的钯配合物。P-立体双膦冠醚适用于钯催化芳基硼酸与α，β-不饱和酮的不对称1，4-加成反应。该反应进行顺利，得到了相应的1，4-加成产物，产率高，对映体选择性好。
A practical synthetic route for enantiomerically pure P-stereogenic diphosphacrowns was developed by using a P-stereogenic bisphosphine as a chiral building block. Their molecular structures were confirmed by NMR spectroscopy and X-ray crystallography. Complexation of the diphosphacrowns with palladium was carried out, and the corresponding palladium complexes were obtained. The P-stereogenic diphosphacrowns were applicable to the chiral ligand for the asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated ketone catalyzed by palladium. This reaction proceeded smoothly to afford the corresponding 1,4-addition products in high yield with good enantioselectivities.