Electrifying P(V): Access to Polar and Radical Reactivity

Area of Science:

• Organic Chemistry
• Electrochemistry
• Organophosphorus Chemistry

Background:

• Hydrophosphorylation is a key reaction in organophosphorus chemistry.
• Developing stereoselective methods for hydrophosphorylation remains a challenge.
• Electrochemical synthesis offers a sustainable and tunable approach for organic transformations.

Purpose of the Study:

• To disclose an electrochemical, fully stereoselective P(V)-radical hydrophosphorylation method.
• To enable the synthesis of valuable organophosphorus compounds from readily available starting materials.
• To investigate the chemoselective nature of the reaction for both olefins and carbonyl compounds.

Main Methods:

• Electrochemical synthesis utilizing a phosphorus(V) reagent.
• Strategic selection of anode materials to control reaction pathways.
• Stereoselective hydrophosphorylation of olefins and carbonyl compounds.

Main Results:

• Achieved fully stereoselective P(V)-radical hydrophosphorylation of olefins.
• Demonstrated a distinct polar pathway for ketone hydrophosphorylation by anode selection.
• Successfully controlled reactivity and selectivity through electrochemical parameters.

Conclusions:

• The developed electrochemical method provides a versatile and stereoselective route to hydrophosphorylated products.
• Anode material selection is crucial for accessing different reaction mechanisms (radical vs. polar).
• This work expands the synthetic utility of electrochemistry in organophosphorus chemistry.