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Abstract：
The Mitsunobu reaction is a powerful transformation for the one-pot activation and substitution of aliphatic alcohols. Significant efforts have focused on modifying the classic conditions to overcome problems associated with purification from phosphine-based byproducts. Herein, we report a phosphine free method for alcohol activation and substitution that is mediated by sulfuryl fluoride. This new method is effective for a wide range of primary alcohols using phthalimide, di-tert-butyl-iminodicarboxylate, and aromatic thiol nucleophiles in 74 % average yield. Activated carbon nucleophiles and a deactivated phenol were also effective for this reaction in good yields. Secondary alcohols were also successful substrates using aryl thiols, affording the corresponding sulfides in 56 % average yield with enantiomeric ratios up to 99:1. This new protocol has a distinct synthetic advantage over many existing phosphine-based methods as the byproducts are readily separable. This feature was exploited in several examples that did not require chromatography for purification. Furthermore, the mild reaction conditions enabled further in situ derivatization for the one-pot conversion of alcohols to amines or sulfones. This method also provides a boarder nucleophile scope compared to existing phosphine-free methods.
摘要：
Mitsunobu反应是一锅活化和取代脂肪醇的有力转变。显著的努力集中于修改经典条件以克服与从基于膦的副产物纯化相关的问题。在这里，我们报道了由硫酰氟介导的醇活化和取代的无膦方法。这种新方法对于使用邻苯二甲酰亚胺的各种伯醇是有效的，亚氨基二甲酸二叔丁酯，和芳族硫醇亲核试剂的平均收率为74%。活性炭亲核试剂和失活的苯酚也以良好的产率有效地用于该反应。仲醇也是使用芳基硫醇的成功底物，以56％的平均收率提供相应的硫化物，对映体比例高达99：1。与许多现有的基于膦的方法相比，这种新方案具有明显的合成优势，因为副产物易于分离。在不需要色谱纯化的几个实施例中利用了该特征。此外，温和的反应条件能够进一步原位衍生化以将醇一锅转化为胺或砜。与现有的无膦方法相比,该方法还提供了更大的亲核试剂范围。
