Pseudocyclic Arylbenziodoxaboroles: Efficient Benzyne Precursors Triggered by Water at Room Temperature
Pseudocyclic Arylbenziodoxaboroles: Efficient Benzyne Precursors Triggered by Water at Room Temperature
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DOI：
10.1002/chem.201704393
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发表时间：
2017-11-27
影响因子：
4.3
通讯作者：
Zhdankin, Viktor V.
中科院分区：
文献类型：
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作者：
Yoshimura, Akira;Fuchs, Jonathan M.;Zhdankin, Viktor V.
以1-乙酰氧基苯并碘硼杂环戊烯和芳烃为原料，在温和条件下与三氟甲磺酸反应，合成了新型有机高价碘化合物芳基苯并碘硼杂环戊烯三氟甲磺酸酯。这些化合物的单晶X射线晶体学显示了假环结构，苯并碘杂硼杂环中的氧和碘之间具有2.698至2.717 A的短分子内相互作用。这些新的假环芳基碘鎓盐在室温下用水处理时容易产生芳炔中间体。生成的芳炔中间体与各种底物反应，以中等至良好的产率得到相应的芳炔加合物。此外，新的苯炔前体还可以作为芳环的芳基化试剂。由芳基苯并碘杂硼杂环戊烯三氟甲磺酸酯产生的芳炔中间体选择性地与叔丁基苯酚反应，形成中等产率的邻位芳基化产物。
New organohypervalent iodine compounds, arylbenziodoxaborole triflates, were prepared from 1-acetoxybenziodoxaboroles and arenes by treatment with trifluoromethanesulfonic acid under mild conditions. Single crystal X-ray crystallography of these compounds revealed a pseudocyclic structure with a short intramolecular interaction of 2.698 to 2.717 A between oxygen and iodine in the benziodoxaborole ring. These new pseudocyclic aryliodonium salts readily generate aryne intermediates upon treatment with water at room temperature. The generated aryne intermediates react with various substrates to give the corresponding aryne adducts in moderate to good yields. Furthermore, the new benzyne precursors can also work as arylating reagents towards aromatic rings. The aryne intermediates generated from arylbenziodoxaborole triflates selectively react with tert-butyl phenol forming products of ortho arylation in moderate yields.