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Ambiphilic cross-coupling with aryl-bismuth reagents.
Byeongdo Roh1, Benedict A Williams1, Josep Cornella2
1Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr, Germany.
Nature
|April 9, 2026
Summary
Researchers developed ambiphilic aryl-bismuth reagents for transition metal-catalyzed cross-coupling reactions. These reagents can act as both nucleophiles and electrophiles, challenging traditional mechanistic assumptions in aryl-aryl bond formation.
Area of Science:
- Organic Chemistry
- Organometallic Chemistry
- Catalysis
Background:
- Cross-coupling reactions form aryl-aryl bonds using transition metal catalysis.
- Reactivity relies on distinct nucleophilic and electrophilic aryl partners.
- Mechanistic roles are typically dictated by intrinsic bond polarity.
Purpose of the Study:
- To introduce ambiphilic aryl-bismuth reagents.
- To demonstrate their dual nucleophilic and electrophilic reactivity in cross-coupling.
- To challenge established mechanistic paradigms in cross-coupling chemistry.
Main Methods:
- Synthesis of novel aryl-bismuth compounds.
- Investigation of their reactivity in transition metal-catalyzed cross-coupling reactions.
- Stoichiometric and mechanistic studies to elucidate reaction pathways.
Main Results:
- Demonstrated that aryl-bismuth reagents can act as both nucleophiles and electrophiles.
- Showcased their ability to undergo both oxidative addition and transmetalation.
- Established a new class of ambiphilic reagents for cross-coupling.
Conclusions:
- Aryl-bismuth reagents break the traditional dichotomy of nucleophilic/electrophilic roles.
- This ambiphilic reactivity challenges the assumption that bond polarity dictates mechanistic function.
- Opens new avenues for designing cross-coupling reactions with unprecedented flexibility.
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