Carbon monoxide as the key: carbonylation triggered (hetero)aryl migration transformations

Area of Science:

• Organic Chemistry
• Synthetic Methodology
• Radical Chemistry

Background:

• Carbonylative functionalization is crucial for synthesizing complex organic molecules.
• Radical reactions offer unique pathways for bond formation and functional group manipulation.
• Allylic alcohols present challenges in selective functionalization.

Purpose of the Study:

• To review recent advances in radical-mediated carbon monoxide (CO) insertion for carbonylative functionalization.
• To highlight the role of CO insertion in carbon chain elongation and allylic alcohol activation.
• To discuss various radical triggers and their impact on migration reactions.

Main Methods:

• Systematic review of literature on radical-mediated CO insertion and migration reactions.
• Analysis of diverse radical triggers (e.g., CF3, diazo-derived, N-centered).
• Discussion of mechanistic insights into the interplay of CO insertion and migration.

Main Results:

• Demonstration of remote aryl/heteroaryl transfer to carbonyl carbons.
• Synthesis of valuable 1,4-dicarbonyl compounds and lactones.
• Activation of challenging allylic alcohol substrates via radical migration.

Conclusions:

• Radical-mediated CO insertion coupled with migration offers a powerful tool for synthesizing functionalized scaffolds.
• Mild reaction conditions and broad substrate scope are key advantages.
• Future directions include expanding migration scope, simplifying design, and developing asymmetric catalysis.