Nickel-Catalyzed Twofold Conjunctive Coupling via Philicity-Alternating Radical Relay.

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Methodology

Background:

• Forming multiple and remote carbon-carbon bonds is synthetically challenging due to control over reactivity and selectivity.
• Existing methods often struggle with complex bond formations requiring precise control.

Purpose of the Study:

• To develop a novel nickel-catalyzed twofold conjunctive cross-electrophile coupling reaction.
• To enable the formation of multiple C-C bonds using alkenes and 1,3-enynes as platforms.

Main Methods:

• Nickel-catalyzed twofold conjunctive cross-electrophile coupling.
• Utilizing alkenes and 1,3-enynes as conjunctive platforms with alkyl and aryl halides.
• Employing a philicity-alternating radical relay followed by selective radical capture.

Main Results:

• Enabled the formation of three or more C-C bonds through a sequential radical addition and capture mechanism.
• Experimental and theoretical studies elucidated the reaction pathway, including radical additions to π systems.
• Demonstrated the formation of complex molecules via a five-component coupling reaction.

Conclusions:

• The developed twofold conjunctive coupling offers a versatile strategy for constructing complex molecular architectures.
• The reaction provides a powerful tool for synthetic chemists, overcoming limitations in C-C bond formation.
• The study highlights the potential of nickel catalysis in achieving challenging synthetic transformations.