Photoinduced Copper-Catalyzed Asymmetric Three-Component Radical 1,2-Azidooxygenation of 1,3-Dienes

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Methodology

Background:

• Multicomponent difunctionalization of 1,3-dienes offers efficient synthesis of allylic compounds.
• Challenges remain in expanding radical scope and achieving enantiocontrol in these reactions.

Purpose of the Study:

• To develop a highly enantioselective three-component radical 1,2-azidooxygenation of 1,3-dienes.
• To address limitations in radical scope and enantiocontrol for synthesizing chiral allylic compounds.

Main Methods:

• Utilized a photoinduced copper-catalyzed reaction involving 1,3-dienes, azidobenziodazolone, and carboxylic acids.
• Employed a chiral copper complex as a bifunctional catalyst for radical generation and C-O cross-coupling.

Main Results:

• Achieved unprecedented highly enantioselective three-component radical 1,2-azidooxygenation.
• Demonstrated broad substrate scope, high functional group tolerance, and excellent chemo-, regio-, and enantioselectivity.
• Provided practical access to diverse azidated chiral allylic esters.

Conclusions:

• The developed protocol offers a mild and efficient route to valuable chiral allylic compounds.
• The chiral copper complex plays a crucial role in both photoredox catalysis and asymmetric induction.
• This work significantly advances the field of enantioselective difunctionalization of 1,3-dienes.