Asymmetric versus C2-symmetric ligands:: Origin of the enantioselectivity in ruthenium-pybox-catalyzed cyclopropanation reactions

被引:25
作者
Cornejo, A
Fraile, JM
García, JI
Gil, MJ
Martínez-Merino, V
Mayoral, JA
Salvatella, L
机构
[1] Univ Zaragoza, CSIC, Inst Ciencia Mat Aragon, E-50009 Zaragoza, Spain
[2] Univ Zaragoza, CSIC, Inst Catalisis Homogenea, E-50009 Zaragoza, Spain
[3] Univ Publ Navarra, Dept Quim Aplicada, Pamplona 31006, Spain
关键词
asymmetric catalysis; density functional calculations; enantioselectivity; N ligands; ruthenium;
D O I
10.1002/anie.200461418
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
(Figure Presented) One stereogenic center suffices in pyridinebis(oxazoline) (pybox) ligands for efficient ruthenium-catalyzed cyclopropanation. A molecular-modeling study reveals the main origin of the enantioselectivity to be unfavorable steric interactions between the substituent on pybox and styrene in a Si approach to the carbene intermediate (see picture).
引用
收藏
页码:458 / 461
页数:4
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