Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.
Chemistry. 2020 Jan 16;26(4):783-787. doi: 10.1002/chem.201903570. Epub 2019 Sep 30.
An unprecedented S-N variant of the benzidine rearrangement for construction of biaryls has been developed. Aryl sulfoxides underwent dehydrogenative coupling with anilines by successive treatment with trifluoromethanesulfonic anhydride and trifluoromethanesulfonic acid to provide the corresponding 2-amino-2'-sulfanyl- and/or 4-amino-4'-sulfanylbiphenyls. Mechanistic studies indicate that the C-C-bond-forming sigmatropic rearrangement proceeds intramolecularly from dicationic S-N-tethered species.
一种前所未有的苯二胺重排 S-N 变体已被开发用于构建联苯。芳基砜与苯胺通过三氟甲磺酸酐和三氟甲磺酸的连续处理进行脱氢偶联，以提供相应的 2-氨基-2'-硫基-和/或 4-氨基-4'-硫基联苯。机理研究表明，C-C 键形成的西格玛重排从二阳离子 S-N 键合的物种进行分子内反应。
