Structural reevaluation of the electrophilic hypervalent iodine reagent for trifluoromethylthiolation supported by the crystalline sponge method for X-ray analysis.
Structural reevaluation of the electrophilic hypervalent iodine reagent for trifluoromethylthiolation supported by the crystalline sponge method for X-ray analysis.
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DOI：
10.1002/anie.201310897
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发表时间：
2014-03-17
影响因子：
16.6
通讯作者：
Buchwald, Stephen L.
中科院分区：
文献类型：
--
作者：
Vinogradova, Ekaterina V.;Mueller, Peter;Buchwald, Stephen L.
关键词：
高价碘 λ3-苯并杂环戊烯是常见的亲电子转移试剂，与其非环状类似物相比，以其增强的稳定性而闻名。在此，我们提供的数据表明，氯代苯并阿多索与两种不同的硫醇盐亲核试剂（硫氰酸盐和三氟甲基硫醇盐）反应，导致形成稳定的硫过氧复合物，而不是预期的苯并阿多索衍生物。我们进一步报告了先前描述的亲电子三氟甲基硫基化试剂 (1) 的修改结构，该试剂先前被认为含有苯并氧杂环戊烯骨架。我们的研究结果基于分析技术的结合，包括最近引入的用于 X 射线分析的结晶海绵方法，明确地证明 1 在溶液和固态下都是硫过氧化合物。
Hypervalent iodine λ3-benziodoxoles are common electrophilic transfer reagents known for their enhanced stability compared to their non-cyclic analogues. Herein we present data showing that chlorobenziodoxole reacts with two different thiolate nucleophiles (thiocyanate and trifluoromethylthiolate), resulting in the formation of stable thioperoxy complexes rather than the expected benziodoxole derivatives. We further report a revised structure for the earlier described electrophilic trifluoromethylthiolation reagent (1), which was previously believed to contain the benziodoxole framework. Our findings, which are based on a combination of analytical techniques, including the recently introduced crystalline sponge method for X-ray analysis, unambiguously demonstrate that 1 is a thioperoxy compound both in solution and the solid state.
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影响因子：
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作者：
Frei, Reto;Waser, Jerome
通讯作者：
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影响因子：
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作者：
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KATRITZKY, AR;GALLOS, JK;DURST, HD
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通讯作者：
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