Abstract

Traditional methods for C–P bond formation via direct addition of P–H species to unsaturated compounds are usually implemented in the presence of base and metal catalysts or radical initiators in various organic solvents. During the last five years, a novel efficient and general catalyst/initiator- and solvent-free version of the hydrophosphination and hydrophosphinylation of multiple C–C bonds with H-phosphines and their chalcogenides has begun to develop and it is attracting growing attention. This approach corresponds to the recently emerged pot-, atom-, and step-economy (PASE) green paradigm. This review covers the literature on the synthesis of useful and in-demand organophosphorus compounds via catalyst- and solvent-free addition of P–H species to alkenes and alkynes.

1 Introduction

2 Addition of Secondary Phosphines to Alkenes

3 Hydrophosphinylation of Alkenes with Secondary Phosphine Chalcogenides

3.1 Oxidative Addition of Phosphine Oxides to Vinyl Sulfides

3.2 Addition of Secondary Phosphine Sulfides and Phosphine Selenides to Alkenes

3.3 Addition of Secondary Phosphine Sulfides and Phosphine Selenides to Divinyl Chalcogenides

3.4 Hydrophosphinylation of Alkenes with Secondary Phosphine/Chalcogen Pair (Three-Component Reactions)

4 Addition of Secondary Phosphines to Alkynes

5 Addition of Secondary Phosphine Chalcogenides to Alkynes

6 Conclusion

Traditional methods for C–P bond formation via direct addition of P–H species to unsaturated compounds are usually implemented in the presence of base and metal catalysts or radical initiators in various organic solvents. During the last five years, a novel efficient and general catalyst/initiator- and solvent-free version of the hydrophosphination and hydrophosphinylation of multiple C–C bonds with H-phosphines and their chalcogenides has begun to develop and it is attracting growing attention. This approach corresponds to the recently emerged pot-, atom-, and step-economy (PASE) green paradigm. This review covers the literature on the synthesis of useful and in-demand organophosphorus compounds via catalyst- and solvent-free addition of P–H species to alkenes and alkynes.

1 Introduction

2 Addition of Secondary Phosphines to Alkenes

3 Hydrophosphinylation of Alkenes with Secondary Phosphine Chalcogenides

3.1 Oxidative Addition of Phosphine Oxides to Vinyl Sulfides

3.2 Addition of Secondary Phosphine Sulfides and Phosphine Selenides to Alkenes

3.3 Addition of Secondary Phosphine Sulfides and Phosphine Selenides to Divinyl Chalcogenides

3.4 Hydrophosphinylation of Alkenes with Secondary Phosphine/Chalcogen Pair (Three-Component Reactions)

4 Addition of Secondary Phosphines to Alkynes

5 Addition of Secondary Phosphine Chalcogenides to Alkynes

6 Conclusion

中文翻译：

---

在烯烃和炔烃中无催化剂和无溶剂的P–H加成：C–P键形成的绿色方法

摘要

通过将P–H物种直接添加到不饱和化合物中形成C–P键的传统方法通常是在各种有机溶剂中存在碱和金属催化剂或自由基引发剂的情况下实施的。在过去的五年中，新型高效且通用的无催化剂/引发剂和无溶剂的多C–C键与H-膦及其硫族化物的加氢磷酸化和氢次膦化反应已开始开发，并引起了越来越多的关注。这种方法对应于最近出现的钾肥，原子和阶梯经济（PASE）绿色范例。这篇综述涵盖了有关通过在烯烃和炔烃中无催化剂和无溶剂加成PH物质来合成有用和需求的有机磷化合物的文献。

1引言

2在烯烃中添加次生膦

3仲膦硫属元素化物对烯烃的氢膦化作用

3.1将氧化膦氧化成乙烯基硫化物

3.2向烯烃中添加次生膦硫化物和硒化膦

3.3在二乙烯基硫属元素化物中添加次生膦硫化物和硒化膦

3.4带有二级膦/硫族元素对的烯烃的氢膦酰化（三组分反应）

4将次生膦类添加到炔烃中

5向炔烃中添加次膦硫属元素化物

六，结论

通过将P–H物种直接添加到不饱和化合物中形成C–P键的传统方法通常是在各种有机溶剂中存在碱和金属催化剂或自由基引发剂的情况下实施的。在过去的五年中，新型高效且通用的无催化剂/引发剂和无溶剂的多C–C键与H-膦及其硫族化物的加氢磷酸化和氢次膦化反应已开始开发，并引起了越来越多的关注。这种方法对应于最近出现的钾肥，原子和阶梯经济（PASE）绿色范例。这篇综述涵盖了有关通过在烯烃和炔烃中无催化剂和无溶剂加成PH物质来合成有用和需求的有机磷化合物的文献。

1引言

2在烯烃中添加次生膦

3仲膦硫属元素化物对烯烃的氢膦化作用

3.1将氧化膦氧化成乙烯基硫化物

3.2向烯烃中添加次生膦硫化物和硒化膦

3.3在二乙烯基硫属元素化物中添加次生膦硫化物和硒化膦

3.4带有二级膦/硫族元素对的烯烃的氢膦酰化（三组分反应）

4将次生膦类添加到炔烃中

5向炔烃中添加次膦硫属元素化物

六，结论