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用于制备氮杂环丙烷以及在室温下由重氮乙酸乙酯对映选择性形成环丙烷的单体铑(II)催化剂。

Monomeric rhodium(II) catalysts for the preparation of aziridines and enantioselective formation of cyclopropanes from ethyl diazoacetate at room temperature.

作者信息

Krumper J R, Gerisch M, Suh J M, Bergman R G, Tilley T D

机构信息

Department of Chemistry and Center for New Directions in Organic Synthesis (CNDOS), University of California, Berkeley, California 94720, USA.

出版信息

J Org Chem. 2003 Dec 12;68(25):9705-10. doi: 10.1021/jo035120e.

Abstract

A family of bis(oxazoline) complexes of coordinatively unsaturated monomeric rhodium(II) (2a,b, 3a,b) are described. These complexes serve as catalysts for cyclopropanation of olefins by ethyl diazoacetate, giving excellent yields (66-94%). Enantioselectivities for the cis product isomers are good (61-84%). The reaction shows an unusual preference for formation of the cis isomers. Catalytic aziridination of N-aryl imines with ethyl diazoacetate is also described.

摘要

描述了一类配位不饱和单体铑(II)的双(恶唑啉)配合物(2a、b,3a、b)。这些配合物可作为由重氮乙酸乙酯进行烯烃环丙烷化反应的催化剂,产率优异(66 - 94%)。顺式产物异构体的对映选择性良好(61 - 84%)。该反应对顺式异构体的形成表现出异常的偏好。还描述了用重氮乙酸乙酯对N - 芳基亚胺进行催化氮杂环丙烷化反应。

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