A flow-microreactor approach to protecting-group-free synthesis using organolithium compounds
A flow-microreactor approach to protecting-group-free synthesis using organolithium compounds
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DOI：
10.1038/ncomms1264
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发表时间：
2011-04-01
影响因子：
16.6
通讯作者：
Yoshida, Jun-ichi
中科院分区：
文献类型：
--
作者：
Kim, Heejin;Nagaki, Aiichiro;Yoshida, Jun-ichi
在理想合成和绿色可持续发展的背景下，无保护基合成是近年来的研究热点。通常，有机锂物质与酮反应非常迅速，因此如果酮羰基不参与所需的转化，则在有机锂反应之前应保护酮羰基。如果有机锂化学能够摆脱这样的限制，它的力量将大大增强。在这里，我们表明，流动微反应器，使这种保护基团的自由有机锂反应，大大减少了停留时间（0.003秒或更少）。带有酮羰基的芳基锂物质是通过相应的芳基碘与均三甲苯锂的碘锂交换反应产生的，并使用流动微反应器系统与各种亲电试剂反应。该方法已成功地应用于Pauciflorol F的形式合成。
Protecting-group-free synthesis has received significant recent research interest in the context of ideal synthesis and green sustainable chemistry. In general, organolithium species react with ketones very rapidly, and therefore ketone carbonyl groups should be protected before an organolithium reaction, if they are not involved in the desired transformation. If organolithium chemistry could be free from such a limitation, its power would be greatly enhanced. Here we show that a flow microreactor enables such protecting-group-free organolithium reactions by greatly reducing the residence time (0.003 s or less). Aryllithium species bearing ketone carbonyl groups are generated by iodine-lithium exchange reactions of the corresponding aryl iodides with mesityllithium and are reacted with various electrophiles using a flow-microreactor system. The present method has been successfully applied to the formal synthesis of Pauciflorol F.