Hypervalent Iodine/Triflate Hybrid Benzdiyne Equivalents: Access to Controlled Synthesis of Polycyclic Aromatic Compounds
Hypervalent Iodine/Triflate Hybrid Benzdiyne Equivalents: Access to Controlled Synthesis of Polycyclic Aromatic Compounds
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DOI：
10.1021/jacs.7b04483
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发表时间：
2017-06-28
影响因子：
15
通讯作者：
Oyamada, Juzo
中科院分区：
文献类型：
--
作者：
Kitamura, Tsugio;Gondo, Keisuke;Oyamada, Juzo
由2，4，5-三氯苯酚钠制备1，4-苯二炔等价物[2，5-双（三甲基硅基）-4-（三氟甲氧基）苯基]（苯基）碘鎓三氟甲磺酸盐。用氟离子处理后，观察到从苯基碘离子基团一侧化学选择性生成芳炔。本文报道了1，4-苯并二炔与不同亲芳体的一锅双环加成反应，高产率地得到了双环加合物。类似地，由2，3，6-三氯苯酚钠制备带有苯基碘和三氟甲磺酸酯基团的1，3-苯二炔等价物。1，3-苯二炔等价物也经历了化学选择性逐步生成芳炔和与不同亲芳体的双环加成反应。这些杂化苯并二炔等价物提供了高产率的双环加合物，并使得方便的一锅法合成多环芳香族化合物成为可能。
The 1,4-benzdiyne equvalent, [2,5-bis(trimethylsilyl)-4-(trifyloxy)phenyl](phenyl)iodonium triflate, was prepared from sodium 2,4,5-trichlorophenoxide. The chemoselective generation of an aryne from the side of the phenyliodonio group was observed after treatment with a fluoride ion. Double cycloaddition of 1,4-benzdiyne with different arynophiles was conducted in one pot, giving bis-cycloadducts in high yields. Similarly, the 1,3-benzdiyne equivalent bearing phenyliodonio and triflate groups was prepared from sodium 2,3,6-trichlorophenoxide. The 1,3-benzdiyne equivalent also underwent the chemoselective stepwise generation of arynes and the double cycloaddition with different arynophiles. These hybrid benzdiyne equivalents provided the double cycloadducts in high yields and enabled the convenient one-pot procedure for synthesis of polycyclic aromatic compounds.