Generation of Aryl Radicals through Reduction of Hypervalent Iodine(III) Compounds with TEMPONa: Radical Alkene Oxyarylation
Generation of Aryl Radicals through Reduction of Hypervalent Iodine(III) Compounds with TEMPONa: Radical Alkene Oxyarylation
复制标题
DOI：
10.1002/chem.201504852
复制
发表时间：
2016-03-01
影响因子：
4.3
通讯作者：
Studer, Armido
中科院分区：
文献类型：
--
作者：
Hartmann, Marcel;Li, Yi;Studer, Armido
报道了一种以2，2，6，6-四甲基哌啶-1-氧基钠（TEMPONa）为单电子转移（SET）还原剂，从二芳基碘鎓盐和碘亚甲基丙二酸盐中选择性生成芳基自由基的新方法。在各种烯烃的存在下，在高价碘化合物的SET还原之后形成的芳基自由基经历烯烃加成，并且由此产生的加合物自由基被伴随产生的克里思自由基有效地捕获，以最终以中等至非常好的产率提供氧芳基化产物。研究了各种碘（III）试剂的芳基生成效率，并通过计算方法研究了碘亚甲基丙二酸酯芳基的生成。
A novel method for selective generation of aryl radicals from diaryliodonium salts and iodanylidene malonates with sodium 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPONa) as a single-electron transfer (SET) reducing reagent is described. In the presence of various alkenes, aryl radicals formed after SET-reduction of hypervalent iodine compounds undergo alkene addition and the adduct radicals that are thus generated are efficiently trapped by the concomitantly generated TEMPO radical to eventually afford oxyarylated products in moderate to very good yields. The efficiency of aryl radical generation of various iodine(III) reagents is studied and the generation of an iodanylidene malonate aryl radical is also investigated by computational methods.