Polarity Transduction Enables the Formal Electronically Mismatched Radical Addition to Alkenes

Area of Science:

• Organic Chemistry
• Synthetic Chemistry

Background:

• Carbon-carbon bond formation is crucial in organic synthesis.
• Traditional methods for radical addition to alkenes require specific electronic properties (polarity matching), limiting their scope.
• Electron-deficient alkenes are typically required for reactions with alkyl radicals.

Purpose of the Study:

• To introduce a novel polarity transduction strategy to overcome electronic limitations in radical alkene additions.
• To enable the formation of carbon-carbon bonds with a broader range of substrates.
• To demonstrate a new method for synthesizing complex molecules.

Main Methods:

• Utilizing vinyl sulfonium ions as reaction partners for carbon-centered radicals.
• Employing a polarity transduction approach to circumvent traditional electronic requirements.
• Investigating in situ or sequential nucleophilic displacement of adducts.

Main Results:

• Vinyl sulfonium ions react with carbon-centered radicals to form adducts.
• These adducts can be further functionalized via nucleophilic displacement.
• The strategy successfully derivatized unmodified complex bioactive molecules, showcasing broad generality.

Conclusions:

• The polarity transduction strategy effectively broadens the scope of radical carbon-carbon bond formation.
• This method provides access to compounds previously unattainable through conventional synthetic routes.
• The approach is versatile and applicable to the modification of intricate bioactive molecules.