Programmable divergent electrochemical ring-opening multifunctionalization of strained rings.

Area of Science:

• Organic Chemistry
• Electrochemistry
• Synthetic Methodology

Background:

• Ring-opening functionalization of strained rings is valuable but challenging.
• Existing methods struggle with selective control over multiple inert C-H/C-C bonds.
• Site, regio, and oxidation state control remain unmet challenges.

Purpose of the Study:

• To develop a multisite programmable, divergent ring-opening functionalization strategy.
• To overcome limitations in selective C-H/C-C bond functionalization.
• To enable facile synthesis of diverse multi-oxygenated scaffolds.

Main Methods:

• Electro-oxidation of continuous C-C bonds and multiple C(sp3)-H bonds.
• Controlled generation of olefins via an 'olefin slow-release pool' to ensure selectivity.
• Utilizing direct current electrolysis, rapid alternating polarity electrolysis, and electrophotocatalysis.

Main Results:

• Achieved precise trioxygenation, tetraoxygenation, and trihalohydroxylation.
• Demonstrated controllable remote alkenylation.
• Successfully transformed strained rings into diverse scaffolds like oxazolines, polyols, and polyhalogenated alcohols.

Conclusions:

• The developed method offers a versatile approach for strained ring functionalization.
• Enables the synthesis of complex multi-oxygenated structures and bicyclic frameworks.
• Provides a powerful tool for skeletal editing and accessing novel chemical architectures.