Organophosphorus compounds have numerous useful applications, from versatile ligands and nucleophiles in the case of trivalent organophosphorus species to therapeutics, agrochemicals and material additives for pentavalent species. Although phosphorus chemistry is a fairly mature field, the construction of C–P(V) bonds relies heavily on either prefunctionalized substrates such as alkyl or aryl halides, or requires previously oxidized bonds such as C=N or C=O, leading to potential sustainability issues when looking at the overall synthetic route. In light of the recent advances in photochemistry, using photons as a reagent can provide better alternatives for phosphorylations by unlocking radical mechanisms and providing interesting redox pathways. This review will showcase the different photomediated phosphorylation procedures available for converting C–H bonds into C–P(V) bonds.

1 Introduction

1.1 Organophosphorus Compounds

1.2 Phosphorylation: Construction of C–P(V) Bonds

1.3 Photochemistry as an Alternative to Classical Phosphorylations

2 Ionic Mechanisms Involving Nucleophilic Additions

3 Mechanisms Involving Radical Intermediates

3.1 Mechanisms Involving Reactive Carbon Radicals

3.2 Mechanisms Involving Phosphorus Radicals

3.2.1 Photoredox: Direct Creation of Phosphorus Radicals

3.2.2 Photoredox: Indirect Creation of Phosphorus Radicals

3.2.3 Dual Catalysis

3.3 Photolytic Cleavage

4 Conclusion and Outlook

有机磷化合物有许多有用的应用，从三价有机磷物种的通用配体和亲核试剂到五价物种的治疗剂，农药和材料添加剂。尽管磷化学是一个相当成熟的领域，但是C–P（V）键的构建在很大程度上依赖于预官能化的底物（例如烷基卤或芳基卤化物），或者需要预先氧化的键（例如C = N或C = O），从而导致潜在的考察整体综合路线时的可持续性问题。鉴于光化学的最新进展，使用光子作为试剂可通过解锁自由基机制并提供有趣的氧化还原途径为磷酸化提供更好的替代方法。

1引言

1.1有机磷化合物

1.2磷酸化：C–P（V）键的构建

1.3用光化学替代经典的磷酸化

2离子机制涉及亲核加成。

3种涉及自由基中间体的机制

3.1涉及活性碳自由基的机理

3.2涉及磷自由基的机理

3.2.1光氧化还原：直接产生磷自由基

3.2.2光氧化还原：间接产生磷自由基

3.2.3双催化

3.3光解

4结论与展望