Abstract：
The diarylation and skeletal diversification of unstrained cyclic amines was exploited to expand and modify the favorable properties of this important substrate class with pivotal roles in drug discovery. Cyclic amines were employed in the synthesis of a novel class of amino-substituted diaryliodonium salts, which were converted to highly functionalized diarylamines through an atom-efficient one-pot N-arylation/ring opening reaction with external nucleophiles. The reaction proceeds through in situ formation of a diarylammonium intermediate that undergoes a nucleophilic ring opening by cleavage of the strong C-N bond. A wide variety of diarylamines was obtained through introduction of two different aryl groups of varied electronics, and the retained iodo-substituent enables downfield diversifications of the products. More than 20 nucleophiles, including amines, phenols, carboxylic acids, thiols and halides, were alkylated with high functional group tolerance, and the strategy proved efficient also in in late-stage functionalization of natural products and pharmaceuticals.
摘要：
利用无应变环胺的二芳基化和骨架多样化来扩展和修饰该重要底物类别的有利性质，并在药物发现中起关键作用。环胺用于合成新型氨基取代的二芳基碘鎓盐，通过与外部亲核试剂的原子有效的一锅法N-芳基化/开环反应将其转化为高度官能化的二芳基胺。反应通过原位形成二芳基铵中间体进行，该中间体通过强C-N键的裂解而发生亲核开环。通过引入不同电子的两个不同芳基获得了各种各样的二芳基胺，和保留的碘取代基实现产品的低场多样化。超过20种亲核试剂,包括胺,酚类物质,羧酸，硫醇和卤化物，具有高官能团耐受性的烷基化，该策略在天然产物和药物的后期功能化中也被证明是有效的。
