Organobismuth Reagents in Organic Synthesis

Organobismuth reagents occupy a unique niche in modern organic synthesis by combining the low toxicity and cost advantages of bismuth with versatile reactivity profiles. These compounds, characterised by Bi–C bonds and often featuring hypervalent Bi centres, serve as both stoichiometric reagents and catalysts in a variety of bond-forming transformations. Their redox flexibility, typically involving Bi(III)/Bi(V) cycles, enables the construction of C–C, C–O and C–X linkages under mild, environmentally benign conditions. Recent advances have introduced bench-stable bismacycles bearing modular sulfone bridges or heteroatom substitutions, thereby expanding the scope of electrophilic arylation and umpolung strategies. In many cases, organobismuth reagents offer complementary selectivity to conventional transition-metal catalysts, providing access to electron-deficient or sterically hindered substrates without the need for cryogenic temperatures or protecting-group manipulations. The development of scalable, chromatography-free procedures for bismacycle synthesis has further bolstered their appeal for large-scale applications in pharmaceuticals and agrochemicals. Collectively, the field is evolving towards more sustainable protocols that capitalise on bismuth’s benign profile while addressing long-standing challenges in chemoselectivity and process efficiency.

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Organobismuth Reagents in Organic Synthesis publication trend

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Technical terms

Organobismuth reagent: A compound containing a carbon–bismuth bond, used for bond-forming transformations in organic synthesis.

Hypervalent: A description of molecules in which the central atom expands its valence shell beyond the octet rule, often seen in Bi(V) species.

Electrophilic arylation: A reaction in which an electrophilic aryl group is transferred to a nucleophilic site on a substrate, typically mediated by a high-valent metal centre.

Umpolung: A strategy that inverts the normal polarity of a functional group, enabling unconventional bond-forming pathways.

Bismacycle: A cyclic organobismuth compound featuring a multi-membered ring that incorporates a bismuth atom and serves as a bench-stable electrophilic reagent.

Bi(III)/Bi(V) redox cycle: A catalytic mechanism involving interconversion between trivalent and pentavalent bismuth oxidation states to facilitate substrate activation and bond formation.

References

1. Bismuth-Catalyzed Oxidative Coupling of Arylboronic Acids with Triflate and Nonaflate Salts. Journal of the American Chemical Society (2020).
2. Synthesis, Properties Characterization and Applications of Various Organobismuth Compounds. Molecules (2011).
3. Umpolung Synthesis of Pyridyl Ethers by BiV‐Mediated O‐Arylation of Pyridones. Angewandte Chemie International Edition (2022).
4. Development and Scale-Up of a New Sulfone-Based Bismacycle as a Universal Precursor for Bi(V)-Mediated Electrophilic Arylation. Organic Process Research & Development (2024).