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The exploration of novel ruthenium catalytic system for cyclopropanation (II) - Preliminary investigation on selectivity of trans: Cis controlled by stereochemistry of N,P-ligand
Li, C; Zhou, DH; Yao, XQ; Liu, XM; Lu, SW; Han, XW; Bao, XH
关键词Cyclopropanation Molecular Mechanics/dynamics Carbene
刊名CHINESE JOURNAL OF INORGANIC CHEMISTRY
2001-07-15
17期:4页:507-512
收录类别SCI
文章类型Article
WOS标题词Science & Technology ; Physical Sciences
类目[WOS]Chemistry, Inorganic & Nuclear
研究领域[WOS]Chemistry
关键词[WOS]COMPLEXES ; LIGANDS
英文摘要A novel ruthenium catalytic system with 1R, 2R-cyclohexyl-N2P2 as ligand for the asymmetric cyclopropanation of styrene was investigated. Abnormal trans: cis phenomenon was found when the catalytic system was pretreated with AgOTf (silver triflate). The trans: cis is near 1: 1, but the cis-products has a little advantage. The molecular mechanics/dynamics were used to study this phenomenon. The geometric energies of two approaching states, which resulting in trans- and cis-products were compared. The results reveal that the energy of valence terms is not the major factor to decide the trans: cis ratio of cyclopropanation products because the difference on the energy of valence terms is very little (about 0.2kcal (.) mol(-1)), The theoretical calculation by molecular mechanics was in agreement to this result. But as for energy of nonbonding terms, the interaction of Van der waals between intermediate M1 and styrene to give the cis-products is so strong ( - 0.73 kcal (.) mol(-1)) that it offsets the disadvantage caused by elcetrostatic energy. So the total energy of interaction between M1 and styrene is favorable to give cis-products. But the difference of total energy for interaction of M1 and styrene to give trans- and cis-products is small. It is about 2,5kcal (.) mol(-1) This ensures the trans: cis ratio of cyclopropanation products is near 1: I, which is consistent with experimental results and decided by stereochemistry of N, P-ligand.
语种英语
WOS记录号WOS:000169723100008
引用统计
被引频次:1[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/138964
专题中国科学院大连化学物理研究所
作者单位1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China
2.Liaoning Normal Univ, Dept Chem, Dalian 116029, Peoples R China
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GB/T 7714
Li, C,Zhou, DH,Yao, XQ,et al. The exploration of novel ruthenium catalytic system for cyclopropanation (II) - Preliminary investigation on selectivity of trans: Cis controlled by stereochemistry of N,P-ligand[J]. CHINESE JOURNAL OF INORGANIC CHEMISTRY,2001,17(4):507-512.
APA Li, C.,Zhou, DH.,Yao, XQ.,Liu, XM.,Lu, SW.,...&Bao, XH.(2001).The exploration of novel ruthenium catalytic system for cyclopropanation (II) - Preliminary investigation on selectivity of trans: Cis controlled by stereochemistry of N,P-ligand.CHINESE JOURNAL OF INORGANIC CHEMISTRY,17(4),507-512.
MLA Li, C,et al."The exploration of novel ruthenium catalytic system for cyclopropanation (II) - Preliminary investigation on selectivity of trans: Cis controlled by stereochemistry of N,P-ligand".CHINESE JOURNAL OF INORGANIC CHEMISTRY 17.4(2001):507-512.
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