Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Key Laboratory of Molecular-Based Materials, School of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241000, P.R. China.
Chem Asian J. 2010 Feb 1;5(2):309-14. doi: 10.1002/asia.200900307.
An efficient domino cyclization method for the construction of aza-podophyllotoxin/aza-conidendrin derivatives has been established. Reactions of different dienes with aryl halides in the presence of a palladium catalytic system produced different kinds of podophyllotoxin derivatives through a highly regioselective C-H functionalization. Treatment of dienes with aryl halides that have electron-withdrawing substituents on the phenyl ring created aza-podophyllotoxin derivatives by means of the functionalization of the C-H bonds ortho to the C-halide bonds of the incoming aryl halides. The reaction of dienes with 1-iodobenzene or aryl halides that incorporate electron-donating groups produced aza-conidendrin derivatives by means of the functionalization of both sp(3) C-H and sp(2) C-H bonds. The regioselective C-H functionalization for the formation of different pseudo-podophyllotoxin/-conidendrin derivatives is proven by analyses of the (1)H NMR spectra of the products and selective X-ray analyses of the structures of the products. Thus, the palladium-catalyzed domino cyclization of 1,6-dienes for the preparation of aza-podophyllotoxin/aza-conidendrin derivatives can be controlled by selectively controlling the C-H functionalization.
建立了一种高效的多米诺环化方法，用于构建氮杂鬼臼毒素/氮杂船形碱衍生物。在钯催化体系存在下，不同的二烯与芳基卤反应，通过高度区域选择性的 C-H 官能化，生成了不同类型的鬼臼毒素衍生物。用芳基卤处理具有吸电子取代基的二烯，通过对进入的芳基卤的 C-卤键的邻位 C-H 键的官能化，生成氮杂鬼臼毒素衍生物。二烯与 1-碘苯或具有供电子基团的芳基卤反应，通过 sp(3) C-H 和 sp(2) C-H 键的同时官能化，生成氮杂船形碱衍生物。通过对产物的 (1)H NMR 光谱分析和产物结构的选择性 X 射线分析，证明了不同假鬼臼毒素/假船形碱衍生物形成的区域选择性 C-H 官能化。因此，通过选择性控制 C-H 官能化，可以控制钯催化的 1,6-二烯的多米诺环化反应，用于制备氮杂鬼臼毒素/氮杂船形碱衍生物。
