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实现对烃类具有合成实用性的立体选择性C-H胺化反应。

Toward a synthetically useful stereoselective C-H amination of hydrocarbons.

作者信息

Liang Chungen, Collet Florence, Robert-Peillard Fabien, Müller Paul, Dodd Robert H, Dauban Philippe

机构信息

Institut de Chimie des Substances Naturelles, UPR 2301, CNRS, Avenue de la Terrasse, F-91198 Gif-sur-Yvette, France.

出版信息

J Am Chem Soc. 2008 Jan 9;130(1):343-50. doi: 10.1021/ja076519d. Epub 2007 Dec 12.

Abstract

Reaction between a sulfur(VI) compound and an iodine(III) oxidant in the presence of a catalytic quantity (<=3 mol %) of a rhodium(II) catalyst leads to the formation of a chiral metallanitrene of unprecedented reactivity. The latter allows intermolecular C-H amination to proceed in very high yields up to 92% and excellent diastereoselectivities up to 99% with C-H bond containing starting materials as the limiting component. The scope of this C-H functionalization includes benzylic and allylic substrates as well as alkanes. Secondary positions react preferentially, but insertion into activated primary C-H bonds or sterically accessible tertiary sites is also possible. Cooperative effects between the nitrene precursor and the chiral catalyst at the origin of these good results have also been applied to kinetic resolution of racemic sulfonimidamide. This methodology paves the way to the use of Csp3-H bonds as synthetic precursors for the introduction of a nitrogen functionality into selected positions.

摘要

在催化量(<=3 mol%)的铑(II)催化剂存在下,硫(VI)化合物与碘(III)氧化剂之间的反应导致形成具有前所未有的反应活性的手性金属氮宾。后者使得分子间C-H胺化反应能够以高达92%的非常高的产率和高达99%的优异非对映选择性进行,其中含C-H键的起始原料作为限量组分。这种C-H官能化的范围包括苄基和烯丙基底物以及烷烃。仲位优先反应,但插入活化的伯C-H键或空间可及的叔位也是可能的。氮宾前体与手性催化剂之间在这些良好结果产生过程中的协同效应也已应用于外消旋磺酰亚胺酰胺的动力学拆分。这种方法为将Csp3-H键用作将氮官能团引入选定位置的合成前体铺平了道路。

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