Enantioselective Double Carbonylation Enabled by High-Valent Palladium Catalysis

Area of Science:

• Organometallic Chemistry
• Catalysis
• Synthetic Organic Chemistry

Background:

• Palladium-catalyzed carbonylation reactions are vital for synthesizing complex molecules.
• Achieving high yields and selectivities (chemo-, regio-, enantioselectivities) with traditional low-valent palladium catalysis remains a significant challenge.

Purpose of the Study:

• To develop a novel enantioselective carbonylation reaction using a high-valent palladium catalysis strategy.
• To overcome the limitations of classical low-valent palladium catalysis in achieving high selectivity and yield.

Main Methods:

• Employed a chiral sulfoxide phosphine (SOP) ligand for enantioselective catalysis.
• Utilized a high-valent palladium catalysis strategy involving palladium(II) and palladium(IV) intermediates.
• Investigated a double aminocarbonylation reaction pathway.

Main Results:

• Successfully demonstrated an enantioselective double aminocarbonylation reaction.
• Achieved excellent yields and high chemo-, regio-, and enantioselectivities.
• Elucidated the reaction mechanism through experimental and computational studies, highlighting the formation of a palladium(IV) intermediate.

Conclusions:

• The high-valent palladium catalysis strategy offers a powerful approach for enantioselective carbonylation.
• The developed method provides a significant advancement over traditional low-valent palladium catalysis.
• The chiral SOP ligand plays a crucial role in achieving high enantioselectivity.