A Unified Method for Oxidative and Reductive Decarboxylative Arylation with Orange Light-Driven Ir/Ni...

Area of Science:

• Organic Chemistry
• Photocatalysis
• Sustainable Synthesis

Background:

• Carboxylic acids are key building blocks in organic synthesis.
• Current methods for decarboxylative arylation face limitations with challenging substrates due to radical stability.
• Developing versatile catalytic systems is crucial for expanding synthetic accessibility.

Purpose of the Study:

• To develop a novel Ir/Ni metallaphotoredox system for decarboxylative arylation.
• To activate a broad range of carboxylic acids and redox-active esters (RAEs).
• To establish complementary oxidative and reductive decarboxylation methods under similar reaction conditions.

Main Methods:

• Utilized a new Ir(III) photocatalyst and low-energy orange light.
• Employed a dual Ir/Ni metallaphotoredox catalytic system.
• Investigated both oxidative and reductive decarboxylative arylation pathways.

Main Results:

• Demonstrated broad applicability in activating native carboxylic acids and RAEs.
• Achieved complementary oxidative and reductive decarboxylative paradigms under similar conditions.
• Showcased a wide scope of aryl halide and acid coupling partners, including for photosensitive substrates.

Conclusions:

• The developed Ir/Ni system effectively activates challenging carboxylic acid derivatives.
• This method provides a versatile platform for decarboxylative arylation with advantages over existing blue-light systems.
• Enables efficient synthesis of arylated compounds from abundant feedstock molecules.