Electron Upconversion Enables CP and CS Bond Formation Under Mild Oxidative Conditions: A Theoretical Study

Area of Science:

• Organic Chemistry
• Computational Chemistry
• Synthetic Methodology

Background:

• Traditional methods for C-P and C-S bond formation often rely on strong oxidants.
• These oxidants can lead to high-energy intermediates and undesirable side reactions.
• There is a need for more controlled and efficient synthetic strategies.

Purpose of the Study:

• To investigate an alternative mechanism for C-P and C-S bond formation.
• To explore a pathway operating under basic conditions involving electron upconversion.
• To compare the efficiency and selectivity of this new pathway against conventional methods.

Main Methods:

• Utilized density functional theory (DFT) calculations.
• Examined a radical-anionic pathway involving three-electron bond formation.
• Investigated the oxidation step using mild oxidants like molecular oxygen.

Main Results:

• The proposed radical-anionic pathway is thermodynamically and kinetically favored over traditional two-electron routes.
• This mechanism enables C-P and C-S bond construction using only mild oxidants.
• Electron upconversion facilitates a more controlled reaction.

Conclusions:

• Electron-upconversion mechanisms offer a greener and more selective approach to C-P and C-S bond formation.
• This method reduces reliance on strong oxidants, minimizing side reactions.
• The findings pave the way for more sustainable synthetic organic chemistry.