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铑催化的外消旋叔烯丙基三氯乙酰亚胺酯与苯胺的动态动力学不对称转化。

Rhodium-catalyzed dynamic kinetic asymmetric transformations of racemic tertiary allylic trichloroacetimidates with anilines.

机构信息

Department of Chemistry, University of Iowa, Iowa City, 52242, United States.

出版信息

J Am Chem Soc. 2012 May 23;134(20):8380-3. doi: 10.1021/ja302223p. Epub 2012 May 14.

Abstract

The rhodium-catalyzed regio- and enantioselective amination of racemic tertiary allylic trichloroacetimidates with a variety of aniline nucleophiles is a direct and efficient route to chiral α,α-disubstituted allylic N-arylamines. We describe the first dynamic kinetic asymmetric transformations of racemic tertiary allylic electrophiles with anilines utilizing a chiral diene-ligated rhodium catalyst. The method allows for the formation of α,α-disubstituted allylic N-arylamines in moderate to good yields with good to excellent levels of regio- and enantioselectivity.

摘要

铑催化的外消旋三级烯丙基三氯乙酰胺与各种苯胺亲核试剂的区域和对映选择性胺化是一种直接有效的方法,可制备手性α,α-二取代烯丙基 N-芳基胺。我们描述了首次利用手性二烯配体铑催化剂对消旋三级烯丙基亲电试剂与苯胺进行的动态动力学不对称转化。该方法可以在中等至良好的收率下,以良好至优秀的区域和对映选择性形成α,α-二取代烯丙基 N-芳基胺。

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