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一种温和的、二茂铁催化的(杂)芳烃的C-H亚胺化反应。

A mild, ferrocene-catalyzed C-H imidation of (hetero)arenes.

作者信息

Foo Klement, Sella Eran, Thomé Isabelle, Eastgate Martin D, Baran Phil S

机构信息

Department of Chemistry, The Scripps Research Institute , 10550 North Torrey Pines Road, La Jolla, California 92037, United States.

出版信息

J Am Chem Soc. 2014 Apr 9;136(14):5279-82. doi: 10.1021/ja501879c. Epub 2014 Mar 31.

Abstract

A simple method for direct C-H imidation is reported using a new perester-based self-immolating reagent and a base-metal catalyst. The succinimide products obtained can be easily deprotected in situ (if desired) to reveal the corresponding anilines directly. The scope of the reaction is broad, the conditions are extremely mild, and the reaction is tolerant of oxidizable and acid-labile functionality, multiple heteroatoms, and aryl iodides. Mechanistic studies indicate that ferrocene (Cp2Fe) plays the role of an electron shuttle in the decomposition of the perester reagent, delivering a succinimidyl radical ready to add to an aromatic system.

摘要

报道了一种使用新型基于过氧酯的自牺牲试剂和贱金属催化剂进行直接C-H亚胺化的简单方法。所得的琥珀酰亚胺产物可根据需要在原位轻松脱保护,直接得到相应的苯胺。该反应适用范围广,条件极为温和,并且能耐受可氧化和对酸不稳定的官能团、多个杂原子以及芳基碘化物。机理研究表明,二茂铁(Cp2Fe)在过氧酯试剂的分解过程中起到电子穿梭体的作用,传递一个准备加成到芳环体系上的琥珀酰亚胺基自由基。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/defc/4210156/3d7a676038d2/ja-2014-01879c_0001.jpg

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