A General Platform for Aryl/Alkyl Radical Functionalization Enabled by Photoinduced Electron Donor-Acceptor Complex.

Area of Science:

• Organic Chemistry
• Synthetic Methodology
• Photochemistry

Background:

• Organic bromo- and boryl groups are key synthetic building blocks.
• Dibenzothiophenium salts offer selective alternatives to traditional reagents.
• Site-selective functionalization remains a challenge in organic synthesis.

Purpose of the Study:

• To develop a simple, metal-free protocol for site-selective functionalization.
• To utilize photoinduced electron donor-acceptor (EDA) complexes for novel transformations.
• To expand the scope of functionalization to include alkyl alcohols.

Main Methods:

• Formation of a photoinduced EDA complex using sulfonium salts and Hantzsch ester.
• Employing phenylsulfonyl-based SOMO-philes for arene functionalization.
• Applying the platform to convert alkyl alcohols under mild conditions.

Main Results:

• Achieved site-selective functionalization of arenes under mild, uniform conditions.
• Demonstrated diverse aryl/alkyl functionalizations including sulfurization, selenation, and alkylation.
• Showcased excellent functional group compatibility with complex molecules.

Conclusions:

• The developed protocol provides a versatile and efficient metal-free route for aryl and alkyl functionalization.
• This strategy enables site-selective modification of complex bioactive molecules and druglike scaffolds.
• The photoinduced EDA complex approach offers a sustainable alternative for synthetic chemistry.