THE PREPARATION OF ANTHRAQUINONES AND ANTHRACYCLINONES VIA THE REACTION OF HALOARENES AND CYANOPHTHALIDES UNDER ARYNE-FORMING CONDITIONS
THE PREPARATION OF ANTHRAQUINONES AND ANTHRACYCLINONES VIA THE REACTION OF HALOARENES AND CYANOPHTHALIDES UNDER ARYNE-FORMING CONDITIONS
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DOI：
10.1021/jo00235a007
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发表时间：
1987-12-25
影响因子：
3.6
通讯作者：
BIEHL, ER
中科院分区：
文献类型：
--
作者：
KHANAPURE, SP;REDDY, RT;BIEHL, ER
卤代芳烃2a-n和LDA在THF中原位生成芳烃与适当取代的锂化3-氰基-1(3H)-异苯并呋喃酮6a-e进行环反应，得到相应的蒽醌4a-y，产率良好至中等。在大多数涉及不对称芳烃的反应中，可以观察到锂氰眼化合物的区域选择性加成；然而，在那些没有观察到这种加成作用的反应中，区域异构体很容易用闪光柱色谱法分离。自然产生的岛素、地黄酮、大黄酚、紫豆素、蠕虫菌素和链状菌素的短而高效的合成已经取得了相当好的产量。该方法在合成蒽醌的四环中间体10中的应用证明了该方法的实用性。
Annulative reactions of arynes generated in situ from haloarenes 2a-n and LDA in THF with appropriately substituted lithiated 3-cyano-1(3H)-isobenzofuranones 6a-e afford the corresponding anthraquinones 4a-y in good to moderate yields. Regioselective addition of lithiocyanophthalides is observed in most reactions involving unsymmetric arynes; however, in those reactions in which such addition is not observed, the regioisomers are readily separated by flash column chromatography. Short and efficient syntheses of the naturally occurring islandicin, digitopurpone, pachybasin, chrysophanol, ziganein, helminthosporin, and catenarin have been achieved in fair to good yields. The utility of this approach for the synthesis of anthracylinones is demonstrated by its use in the preparation of tetracyclic intermediate 10 for 4-demethoxydaunomycinone synthesis.