Homologative Radical 1,3-Dicarbofunctionalization of Unactivated Alkenes Enabled by Sequential Functional Group...

Area of Science:

• Organic Chemistry
• Synthetic Methodology
• Photochemistry

Background:

• Radical-mediated 1,2-difunctionalization of alkenes has advanced significantly.
• Homologative 1,3-difunctionalization of alkenes remains an underdeveloped area in synthetic chemistry.

Purpose of the Study:

• To develop a novel photoinduced method for the homologative 1,3-dicarbofunctionalization of unactivated alkenes.
• To achieve one-carbon chain elongation via sequential functional group migrations.

Main Methods:

• Utilized photoinduced radical generation.
• Employed tertiary alcohols and heteroarylsulfones as coupling partners.
• Leveraged sequential functional group migrations for chain elongation.

Main Results:

• Successfully achieved one-carbon chain elongation in alkene difunctionalization.
• Synthesized structurally diverse, densely substituted aliphatic ketones.
• Generated medium-sized cyclic scaffolds with exclusive chemo- and regioselectivity.
• Demonstrated tolerance for a broad range of migrating groups (heteroaryl, phenyl, alkenyl).

Conclusions:

• The developed method provides a novel route for homologative 1,3-difunctionalization.
• This approach expands the toolkit for synthesizing complex organic molecules.
• The reaction exhibits broad substrate scope and functional group tolerance, highlighting its synthetic utility.