Selective fluorination of o0 and m-carboranes. Synthesis of 9-monofluoro-, 9,12-difluoro-1,8,9,12-trifluoro-, and 8,9,10,12-tetrafluoro-o-carboranes and 9-monofluoro-, and 9,10-difluoro-m-carboranes. Molecular structure of 8,9,10,12-tetrafluoro-o-carborane
Reaction of o- and m-carboranes 1 with antimonypentafluoride results in replacement of hydrogen by fluorine at the boron atoms, to give in succession 9-fluoro-; 9,12-difluoro-; 8,9,12-trifluoro-; 8,9,10,12-tetrafluoro-o-carboranes and 9-fluoro-; 9,10-difluoro-m-carboranes. An X-ray structural study of the 8,9,10,12-tetrafluoro-o-carborane has been carried out. The compounds synthesized have been characterized
的反应ø -和米-carboranes 1与置换氢五氟化锑的结果通过在氟硼原子,以得到连续9-氟; 9,12-二氟-; 8,9,12-三氟-; 8,9,10,12-四氟邻氨基甲酸酯和9-氟-; 9,10-二氟米-carboranes。已经对8,9,10,12-四氟-邻-碳硼烷进行了X射线结构研究。合成的化合物已通过元素分析和1 H,11 B 1 H},19 F NMR光谱进行了表征。
Palladium-Catalyzed Selective Fluorination of <i>o</i>-Carboranes
作者:Zaozao Qiu、Yangjian Quan、Zuowei Xie
DOI:10.1021/ja405808t
日期:2013.8.21
A Pd(II)-catalyzed direct selective fluorination reaction of carboranes using a F+ reagent has been developed, leading to a series of polyfluorocarboranes in high isolated yields. The mechanism involving electrophilic B-H activation, oxidation of Pd(II) by F+ species, and reductive elimination is proposed.