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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
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Regiodivergent Radical-Relay Alkene Dicarbofunctionalization.
Zhong Liu1, Francesco D'Amico1,2, Ruben Martin1,3
1The Barcelona Institute of Science and Technology, Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona, Spain.
Journal of the American Chemical Society
|October 10, 2024
Summary
This study introduces a novel nickel-catalyzed method for the regioselective difunctionalization of olefins, creating crucial carbon-carbon bonds through a radical relay mechanism.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Methodology
Background:
- Unactivated olefins are challenging substrates for selective functionalization.
- Developing methods for long-range C-C bond formation is essential in organic synthesis.
Purpose of the Study:
- To report a regiodivergent 1,n-dicarbofunctionalization of unactivated olefins.
- To enable the formation of both C(sp3)-C(sp3) and C(sp2)-C(sp3) linkages.
- To achieve this transformation using nickel catalysis and a radical relay.
Main Methods:
- Nickel-catalyzed reaction employing a radical relay mechanism.
- Utilizing unactivated olefins as substrates.
- Investigating the role of ligand backbone in determining site-selectivity.
Main Results:
- Successful regioselective 1,n-dicarbofunctionalization of unactivated olefins.
- Formation of both C(sp3)-C(sp3) and C(sp2)-C(sp3) bonds, including long-range linkages.
- Evidence supporting an intertwined mechanism of atom-transfer radical addition (ATRA) and chain-walking.
Conclusions:
- A versatile Ni-catalyzed radical relay system for olefin difunctionalization has been developed.
- The method allows for the controlled formation of diverse C-C bonds.
- Ligand design is critical for controlling site-selectivity in this radical relay process.
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