Tuned C-H functionalization to construct aza-podophyllotoxin/aza-conidendrin derivatives by means of domino cyclization.
Tuned C-H functionalization to construct aza-podophyllotoxin/aza-conidendrin derivatives by means of domino cyclization.
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DOI：
10.1002/asia.200900307
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发表时间：
2010-02
期刊：
影响因子：
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通讯作者：
Yimin Hu;Yuan Qu;Fenghua Wu;Jinghan Gui;Yun Wei;Qiong Hu;Shaowu Wang
中科院分区：
文献类型：
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作者：
Yimin Hu;Yuan Qu;Fenghua Wu;Jinghan Gui;Yun Wei;Qiong Hu;Shaowu Wang
建立了一种高效的多米诺环化方法，用于构建叠氮-鬼臼毒素/叠氮-百合素衍生物。不同的二烯在钯催化体系下与芳基卤化物反应，通过高度区域选择性的C-H官能化反应生成不同种类的鬼臼毒素衍生物。用苯基环上有吸电子取代基的芳基卤化物处理二烯，通过使进入的芳基卤化物的C-H键与c -卤化物键邻位的官能化，产生了氮杂鬼臼毒素衍生物。二烯与含给电子基团的1-碘苯或芳基卤化物反应，通过sp(3) C-H和sp(2) C-H键的官能化，生成偶氮-共聚物衍生物。通过对产物的氢核磁共振光谱分析和对产物结构的选择性x射线分析，证明了不同伪鬼臼毒素/假假鬼臼毒素衍生物的区域选择性C-H功能化。因此，钯催化1,6-二烯的多米诺骨牌环化可以通过选择性地控制C-H功能化来控制氮杂-鬼臼毒素/氮杂-孢子素衍生物的制备。
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.