Deconstructive Radical-Radical Coupling for Programmable Remote Acylation.

Area of Science:

• Synthetic Organic Chemistry
• Catalysis
• Radical Chemistry

Background:

• Dicarbonyl compounds are crucial building blocks in organic synthesis, particularly for heterocycle construction.
• Existing methods like Stetter, Michael, and Friedel-Crafts reactions have limitations in accessing diverse 1,n-dicarbonyl structures.
• A versatile platform for synthesizing various 1,n-dicarbonyls is currently lacking.

Purpose of the Study:

• To establish a unified and flexible synthetic strategy for accessing a wide range of 1,n-dicarbonyl compounds.
• To demonstrate a novel deconstructive approach utilizing dual photocatalysis and carbene catalysis.
• To showcase the broad applicability and functional group tolerance of the developed method.

Main Methods:

• A radical-promoted deconstructive process was employed.
• Dual catalysis involving photocatalysis and carbene catalysis was utilized.
• The strategy was applied to the synthesis of gamma-amino esters and three-component systems.

Main Results:

• A broad scope of 1,n-dicarbonyl compounds was successfully synthesized.
• The method demonstrated robust functional group tolerance.
• The first enantioselective deconstructive synthesis of 1,5-dicarbonyls was achieved using a chiral N-heterocyclic carbene (NHC) catalyst.

Conclusions:

• The developed unified approach provides an enabling platform for accessing diverse 1,n-dicarbonyls.
• This radical-promoted deconstructive strategy broadens synthetic possibilities in organic chemistry.
• The methodology facilitates the synthesis of valuable intermediates and complex molecular architectures.