Miyamoto Naoki, Koseki Daichi, Sumida Kohei, Elboray Elghareeb E, Takenaga Naoko, Kumar Ravi, Dohi Toshifumi
College of Pharmaceutical Sciences, Ritsumeikan University, 1-1-1, Nojihigashi, Kusatsu Shiga, 525-8577, Japan.
Department of Chemistry, Faculty of Science, South Valley University, Qena 83523, Egypt.
Beilstein J Org Chem. 2024 May 3;20:1020-1028. doi: 10.3762/bjoc.20.90. eCollection 2024.
Diaryliodonium(III) salts are versatile reagents that exhibit a range of reactions, both in the presence and absence of metal catalysts. In this study, we developed efficient synthetic methods for the preparation of aryl(TMP)iodonium(III) carboxylates, by reaction of (diacetoxyiodo)arenes or iodosoarenes with 1,3,5-trimethoxybenzene in the presence of a diverse range of organocarboxylic acids. These reactions were conducted under mild conditions using the trimethoxyphenyl (TMP) group as an auxiliary, without the need for additives, excess reagents, or counterion exchange in further steps. These protocols are compatible with a wide range of substituents on (hetero)aryl iodine(III) compounds, including electron-rich, electron-poor, sterically congested, and acid-labile groups, as well as a broad range of aliphatic and aromatic carboxylic acids for the synthesis of diverse aryl(TMP)iodonium(III) carboxylates in high yields. This method allows for the hybridization of complex bioactive and fluorescent-labeled carboxylic acids with diaryliodonium(III) salts.
二芳基碘鎓（III）盐是用途广泛的试剂，无论在有金属催化剂还是无金属催化剂的情况下，都能发生一系列反应。在本研究中，我们通过（二乙酰氧基碘）芳烃或亚碘酰芳烃与1,3,5 -三甲氧基苯在多种有机羧酸存在下反应，开发了制备芳基（TMP）碘鎓（III）羧酸盐的高效合成方法。这些反应在温和条件下进行，使用三甲氧基苯基（TMP）基团作为助剂，无需添加剂、过量试剂，后续步骤也无需进行抗衡离子交换。这些方案适用于（杂）芳基碘（III）化合物上的多种取代基，包括富电子、缺电子、空间位阻大以及对酸不稳定的基团，以及多种脂肪族和芳香族羧酸，可高产率地合成各种芳基（TMP）碘鎓（III）羧酸盐。该方法能够使复杂的生物活性和荧光标记的羧酸与二芳基碘鎓（III）盐进行杂化。
