title: Synthesis of Functionalized Azacalix[1]arene[3]pyridine Macrocycles from Cu(II)-Mediated Direct Amination Reactions of Arene through High Valent Arylcopper(III) Intermediates.
abstract: Mediated by Cu(ClO4)2in the presence of K3PO4under 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 pKa(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.
authors.affiliation: Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University , Beijing 100084, China.
authors.forename: Yang
authors.initials: Y
authors.lastname: Liu
authors.affiliation: Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University , Beijing 100084, China.
authors.forename: Qian
authors.initials: Q
authors.lastname: Zhang
authors.affiliation: Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University , Beijing 100084, China.
authors.forename: Qing-Hui
authors.initials: QH
authors.lastname: Guo
authors.affiliation: Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University , Beijing 100084, China.
authors.forename: Mei-Xiang
authors.initials: MX
authors.lastname: Wang