Halohydrins bearing a hydroxyl and halide functional group, are privileged building blocks in organic synthesis and could be conveniently converted to other significant organic intermediates such as azidoalcohols, aminoalcohols, and epoxides, all of which are widely used in the synthesis of highly value-added chemicals. Among the approaches to halohydrins, the halohydroxylation of olefins provides a direct and efficient approach. The synthesis of bromohydrins has achieved great progress in recent years. However, the approaches to iodohydrins are still very limited. Our previous studies revealed that DMSO could oxidize halo anions to halo cations under acidic conditions. As our continuous development DMSO-based reactions, we report the iodohydroxylation of olefins by using DMSO and HI generated in situ. In this transformation, DMSO performed versatile roles as an oxidant, a solvent and an oxygen source. This reaction featured with simple operation, mild reaction condition, and wild substrate scope, and provided an efficient method to synthesize iodohydrins. Furthermore, the iodoetheration of olefins was also realized by using DMSO and alcohol as the solvent. A representative procedure for this reaction is as following: The mixture of alkene (0.5 mmol), NaI (0.6 mmol), conc. H2SO4 (1.0 mmol), DMSO (1 mL) and DCE (1 mL) were stirred at 60 degrees C under air. TCL monitor the reaction, and the product had a clear spot in phosphomolybdic acid chromogenic agent. After the reaction was completed, saturated solution of Na2S2O3 (0.5 mL) was added into the system to consume the extra I-2. After cooling down to room temperature, the mixture was diluted with water (10 mL) and extracted with ethyl acetate (10 mLx3). The combined organic extract was washed with saturated solution of NaCl (15 mL), dried over MgSO4, and evaporated in vacuo. The residue was purified by chromatography on silica gel (petroleum ether/ethyl acetate) to afford the desired product.

中文翻译：

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烯烃与 DMSO 的氧化碘羟基化

带有羟基和卤化物官能团的卤代醇是有机合成中的特殊组成部分，可以方便地转化为其他重要的有机中间体，如叠氮醇、氨基醇和环氧化物，所有这些都广泛用于高附加值化学品的合成. 在卤代醇的方法中，烯烃的卤代羟基化提供了一种直接有效的方法。近年来，溴醇的合成取得了很大进展。然而，碘醇的方法仍然非常有限。我们之前的研究表明，DMSO 可以在酸性条件下将卤素阴离子氧化为卤素阳离子。随着我们不断发展基于 DMSO 的反应，我们报告了使用 DMSO 和原位生成的 HI 对烯烃进行碘羟基化。在这次转型中，DMSO 作为氧化剂、溶剂和氧源发挥了多种作用。该反应操作简单，反应条件温和，底物范围广，为合成碘醇提供了一种有效的方法。此外，还以DMSO和醇为溶剂实现了烯烃的碘醚化反应。该反应的代表性程序如下：烯烃（0.5 mmol），NaI（0.6 mmol），浓的混合物。H2SO4(1.0mmol)、DMSO(1mL)和DCE(1mL)在60℃下在空气中搅拌。TCL监测反应，产物在磷钼酸显色剂中有明显斑点。反应完成后，向体系中加入饱和Na2S2O3溶液(0.5mL)以消耗多余的I-2。冷却至室温后，混合物用水(10mL)稀释并用乙酸乙酯(10mL×3)萃取。合并的有机萃取液用饱和NaCl溶液(15mL)洗涤，用MgSO4干燥，真空蒸发。通过硅胶色谱法(石油醚/乙酸乙酯)纯化残余物以提供所需产物。