4,5-Dimethyl-2-Iodoxybenzenesulfonic Acid Catalyzed Site-Selective Oxidation of 2-Substituted Phenols to 1,2-Quinols
4,5-Dimethyl-2-Iodoxybenzenesulfonic Acid Catalyzed Site-Selective Oxidation of 2-Substituted Phenols to 1,2-Quinols
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DOI：
10.1002/anie.201612463
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发表时间：
2017-03-27
影响因子：
16.6
通讯作者：
Ishihara, Kazuaki
中科院分区：
文献类型：
--
作者：
Uyanik, Muhammet;Mutsuga, Tatsuya;Ishihara, Kazuaki
以4，5-二甲基-2-碘氧基苯磺酸和氧酮为催化剂，研究了2-取代苯酚选择性羟基化脱芳构化合成1，2-苯喹酚或其环二聚体的反应。在温和的反应条件下，可以有效地合成天然产物双香草酚和丁香烯C甲醚。此外，在苯酚的2-位引入三烷基硅甲基取代基可以进一步提高反应速度和位置选择性。通过[4+2]环加成反应可以将相应的1，2-喹酚转化为各种有用的结构基元。
A site-selective hydroxylative dearomatization of 2-substituted phenols to either 1,2-benzoquinols or their cyclodimers, catalyzed by 4,5-dimethyl-2-iodoxybenzenesulfonic acid with Oxone, has been developed. Natural products such as biscarvacrol and lacinileneC methyl ether could be synthesized efficiently under mild reaction conditions. Furthermore, both the reaction rate and site selectivity could be further improved by the introduction of a trialkylsilylmethyl substituent at the 2-position of phenols. The corresponding 1,2-quinols could be transformed into various useful structural motifs by [4+2] cycloaddition cascade reactions.