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Base- and Additive-Free Ir-Catalyzed ortho-Iodination of Benzoic Acids: Scope and Mechanistic Investigations
ACS Catalysis ( IF 12.9 ) Pub Date : 2018-01-04 00:00:00 , DOI: 10.1021/acscatal.7b02987
Elis Erbing 1 , Amparo Sanz-Marco 1 , Ana Vázquez-Romero 1 , Jesper Malmberg 2 , Magnus J. Johansson 3 , Enrique Gómez-Bengoa 4 , Belén Martín-Matute 1
Affiliation  

A protocol for the C–H activation/iodination of benzoic acids catalyzed by a simple iridium complex has been developed. The method described in this paper allows the ortho-selective iodination of a variety of benzoic acids under extraordinarily mild conditions in the absence of any additive or base in 1,1,1,3,3,3-hexafluoroisopropanol as the solvent. The iridium catalyst used tolerates air and moisture, and selectively gives ortho-iodobenzoic acids with high conversions. Mechanistic investigations revealed that an Ir(III)/Ir(V) catalytic cycle operates, and that the unique properties of HFIP enables the C–H iodination using the carboxylic moiety as a directing group.

中文翻译:

苯甲酸的无碱和无添加剂Ir催化邻位碘化:范围和机理研究

已经开发了一种由简单铱络合物催化的苯甲酸的C–H活化/碘化的方案。本文描述的方法允许在非常温和的条件下,在没有任何添加剂或碱的情况下,在1,1,1,3,3,3-六氟异丙醇作为溶剂中对多种苯甲酸进行邻位碘化。所用的铱催化剂可耐受空气和湿气,并选择性地以高转化率得到碘苯甲酸。机理研究表明,Ir(III)/ Ir(V)催化循环起作用,并且HFIP的独特性质使得能够使用羧基作为引导基团进行C-H碘化。
更新日期:2018-01-04
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