Fries重排

反应

Fries重排反应是一类重要的有机人名反应，它涉及在催化剂存在下加热时将酚酯转化成邻位或对位酰基酚。适用于该反应的催化剂是布朗斯特酸或路易斯酸，如 HF、AlCl₃, BF₃, TiCl₄, 或 SnCl₄。Fries重排反应为邻位、对位选择性反应，用于酰基酚的制备。¹ 这种有机反应以德国化学家Karl Theophil Fries的名字命名。

图 1. 德国化学家Karl Theophil Fries

光-Fries重排也包括在没有催化剂的情况下，只要紫外光存在，酚酯也可以类似地转化成羟基酮。¹

硫杂-Fries重排涉及在二氯甲烷中氯化铝存在下芳基三氟甲磺酸酯转化为三氟甲磺酸亚砜基酚。²

阴离子磷酸-Fries重排包括将芳基磷酸酯 [ArOP(=O)(OR)₂] 转化为邻羟基芳基膦酸酯[o-HO-Ar-P(=O)(OR)₂]。这种重排产生具有邻位C-P键的酚。³

应用

Fries重排已在以下领域得到应用：

• 研究了离子熔体 [1-丁基-3-甲基咪唑鎓氯铝酸盐 ([BMIm]Cl·xAlCl₃)] 作为溶剂和路易斯酸催化剂的应用。 与苯甲酸苯酯的反应得到邻位和对位-羟基二苯甲酮。⁴

图 2. 对羟基二苯甲酮

• 邻羟基苯乙酮和对羟基苯乙酮（药品生产中有用的中间体）的合成。⁵
• α-生育酚（维生素 E）的全合成。⁶
• 通过TiCl₄催化的Fries重排和直接的区域选择性酰化反应，区域选择性合成邻酰基羟基[2.2]对环烷。⁷
• 合成药物和农用化学中间体、热成像材料和有效的抗病毒剂。⁸
• 通过三氟甲磺酸钪催化酰基萘的Fries重排合成羟基萘酮。⁹
• 用3-甲基-2-丁烯酸芳基酯，通过光-Fries重排和碱催化的分子内oxa-Michael加成反应，光化学一锅法合成 5-、6-和 7-取代的苯并二氢吡喃-4-酮。¹⁰

上述综合方案：

图 3. Oxa Michael加成反应

近期研究和趋势

• 无溶剂、微波介电加热条件下的硫代芳烃的硫杂-Fries重排已得到了研究。⁸
  据报道，光反应性液晶聚合物薄膜经历了轴选择性的光-Fries重排，并且在线性偏振紫外 (LPUV) 光下表现出光诱导的光学各向异性。¹
• Fries重排已用于全合成muricadienin的关键步骤，muricadienin是反式和顺式solamin生物合成中的不饱和推定前体。¹⁰
• 手性二茂铁基磷酸酯的阴离子磷酸-Fries重排产生富含非对映异构体的1,2-P,O-膦酸酯，然后可将其转化为对映体纯的磷烷。¹³
• 报道了负载在二氧化硅或其盐Cs_2.5H_0.5PW₁₂O₄₀ (CsPW)上的杂多酸H₃PW₁₂O₄₀(PW)催化芳基酯的液相-Fries重排反应。¹⁴
• 阴离子磷酸-Fries重排已成功应用于二茂铁化学的研究。¹⁵
• Fries重排用于合成抗病毒类黄酮先导化合物，从 2,6-二甲氧基醌开始。¹⁶

图 4. 二甲氧苯醌

• 杂多酸 H₃PW₁₂O₄₀已被报道用于乙酸苯酯的Fries重排，是一种高效和环境友好的催化剂。¹⁷

图 5. 乙酸苯酯

参考文献

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