Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University , Beijing 100084, China.
J Org Chem. 2016 Nov 4;81(21):10404-10410. doi: 10.1021/acs.joc.6b01448. Epub 2016 Aug 10.
Mediated by Cu(ClO) in the presence of KPO under mild conditions, azacalix[1]arene[3]pyridines underwent arene C-H bond amination with a number of sulfonamides, imides, and saccharin to afford the diverse C-N bond forming products. Based on different reactivity between arylcopper(II) and arylcopper(III) compounds toward nitrogen nucleophiles, the reaction proceeded most likely through arene C-H bond metalation via reactive arylcopper(III) intermediates and their binding to nitrogen anions which were derived from deprotonation of acidic N-H bonds of nitrogen nucleophiles of pK (DMSO) < 17.5 followed by reductive elimination. The study not only provides a convenient and straightforward access to functionalized heteracalixaromatics that are not readily obtained by other means but also enriches our understanding of high valent organocopper chemistry.
在温和条件下，KPO 存在下的 Cu(ClO)介导下，氮杂杯[1]芳烃[3]吡啶与多种磺酰胺、酰亚胺和糖精发生芳基 C-H 键胺化反应，生成多种 C-N 键形成产物。基于芳基铜(II)和芳基铜(III)化合物与氮亲核试剂之间的不同反应性，该反应最有可能通过反应性芳基铜(III)中间体进行芳基 C-H 键金属化，然后与氮阴离子结合，氮阴离子来自酸性 N-H 键的去质子化，pK(DMSO) < 17.5 的氮亲核试剂，然后进行还原消除。该研究不仅为功能化杂杯芳烃提供了一种方便直接的方法，这些芳烃不易通过其他方法获得，而且丰富了我们对高价有机铜化学的理解。
