氯化膦与羟基化合物参与的P(III)→P(V)重排反应研究进展

doi:10.6023/cjoc202406052

摘要/Abstract

五价磷P(V)有机物广泛应用于合成、材料、生物、医药和农业等领域, 其合成方法研究一直吸引着有机化学家的兴趣. 从三价磷P(III)到五价磷P(V)的重排反应[P(III)→P(V)]是合成五价磷有机物的重要策略. 经典的Michaelis- Arbuzov反应通过亲核性亚磷酸酯[P(OR)₃]与卤代烃发生P(III)→P(V)重排反应, 为膦酸酯的合成提供了重要方法. 与此相反, 亲电性氯化膦(ClPR¹R²)与羟基化合物(RA—OH)作用可原位生成RA—O—PR¹R²中间体, 继而发生A—O键断裂和A—P键形成, 从而实现P(III)→P(V)重排, 也为五价磷有机物的合成提供了有效方法. 这两类P(III)→P(V)重排反应都是在磷的强亲氧性驱动下实现的, 具有原子经济性高、底物简单易得等优点. 主要综述了氯化膦与不同类型羟基化合物(如醇、羧酸、肟和羟胺等)的P(III)→P(V)重排反应, 分别用于氧膦、膦酸酯、磷酰胺等五价磷化合物的合成.

关键词: 氯化膦, 羟基化合物, 有机磷化合物, 重排反应

Pentavalent organophosphorus compounds are widely used in synthesis, materials, biology, medicine, agriculture, etc, and their synthetic methods have attracted a long-term interest from organic chemists. The P(III)→P(V) rearrangement from trivalent organophosphorus compounds is an important strategy for the synthesis of pentavalent organophosphorus compounds. The classical Michaelis-Arbuzov reaction, which involves a P(III)→P(V) rearrangement reaction between nucleophilic phosphite (P(OR)₃) and alkyl halides, provides an important method for the synthesis of phosphonates. In contrast, the reaction between electrophilic phosphine chlorides (ClPR¹R²) and hydroxyl containing compounds (RA—OH) generaes a RA—O—PR¹R² intermediate in situ, followed by A—O bond cleavage and A—P bond formation thus to realize P(III)→P(V) rearrangement, also provides an effective synthetic method for pentavalent organophosphorus compounds. Two types of the P(III)→P(V) rearrangement reactions are both driven by the oxophilicity of phosphorus, bearing the advantages of high atom economy and readily available substrates. The P(III)→P(V) rearrangement reactions of phosphine chlorides with different types of hydroxyl containing compounds, such as alcohols, carboxylic acids, oximes, hydroxylamines, etc, for the synthesis of phosphine oxides, phosphonates, and phosphoric amides are mainly reviewed, respectively.

Key words: phosphine chlorides, hydroxyl containing compounds, organophosphorus compounds, rearrangement

引用此文

杨露露, 易翠, 吴佳乐, 张宇轩, 白美琪, 李洋, 徐四龙. 氯化膦与羟基化合物参与的P(III)→P(V)重排反应研究进展[J]. 有机化学, 2024, 44(12): 3639-3646.

Lulu Yang, Cui Yi, Jiale Wu, Yuxuan Zhang, Meiqi Bai, Yang Li, Silong Xu. Progress in the P(III)→P(V) Rearrangement Reaction of Phosphine Chlorides and Hydroxyl Containing Compounds[J]. Chinese Journal of Organic Chemistry, 2024, 44(12): 3639-3646.

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图/表 18

图式1. 几种五价磷有机物的合成策略

Scheme 1. Several synthetic strategies for pentavalent organophosphorus compounds

图式2. 不饱和醇与氯化膦参与的[2,3]重排反应

Scheme 2. [2,3] rearrangement of unsaturated alcohols with phosphine chlorides

图式3. 炔丙醇/联烯醇与二苯基氯化膦参与的[2,3]重排反应

Scheme 3. [2,3] rearrangement of propargyl/allenic alcohols with Ph2PCl

图式4. 丙炔醇型底物1-5与氯化膦参与的[2,3]重排串联反应

Scheme 4. [2,3] rearrangement tandem reaction of propargyl alcohols 1-5 with phosphine chlorides

图式5. 环己烯醇1-7与二苯基氯化膦的[2,3]重排反应

Scheme 5. [2,3] rearrangement of cyclohexenol 1-7 with Ph2PCl

图式6. 链状手性烯丙醇与二苯基氯化膦的[2,3]重排反应

Scheme 6. [2,3] rearrangement of acyclic chiral allylic alcohols with Ph2PCl

图式7. 环丙烯基醇与二苯基氯化膦的[2,3]重排反应

Scheme 7. [2,3] rearrangement of cycloprpenyl alcohols with Ph2PCl

图式8. 贫电子烯丙醇与氯化膦的[2,3]重排反应

Scheme 8. [2,3] rearrangement of electron-poor allylic alcohols with phosphine chlorides

图式9. 苄醇与二苯基氯化膦的脱氧重排反应及机理

Scheme 9. Deoxygenative rearrangement of benzyl alcohols with Ph2PCl and its mechanism

图式10. 高烯丙醇、氯化膦和氟烷基碘的自由基串联反应及机理

Scheme 10. Cascade radical reaction of homoallylic alcohols, phosphine chlorides and fluoroalkyl iodide and its mechanism

图式11. 烷基羧酸与二苯基氯化膦的反应及机理

Scheme 11. Reaction of aliphatic carboxylic acids with Ph2PCl and its mechanism

图式12. 芳基羧酸与氯化膦的脱氧膦酰化反应

Scheme 12. Deoxygenative phosphorylation of aromatic carboxylic acids with Ph2PCl

图式13. 肟和氯化膦反应生成膦酰胺

Scheme 13. Synthesis of phosphinic amides from oximes and phosphine chlorides

图式14. 环丁酮肟与氯化膦的开环重排反应

Scheme 14. Ring-opening rearrangement of cyclobutanone oximes wth phosphine chlorides

图式15. 环丁酮肟与氯化膦反应的可能机理

Scheme 15. Proposed mechanism of reaction between cyclobutanone oximes and phosphine chlorides

图式16. 普通羟胺与氯化膦的反应

Scheme 16. Reaction of hydroxylamine with phosphine chlorides

图式17. (a)理论计算的能量曲线和相对能量(kJ/mol); (b)磷酰基和氨基自由基的自旋密度分布(等值线=0.007)

Scheme 17. (a) Computed energy profiles and the relative energies (kJ/mol); (b) Contours (isovalue=0.007) of the spin density of phosphoryl and amino radicals

图式18. 缺电子苯基羟胺与氯膦的重排反应

Scheme 18. Rearrangement of electron-poor phenylhydroxylamine with phosphine chlorides

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