The first bismuth self-mediated oxidative carbonylative coupling reaction via BiIII/BiV redox intermediates

Zhao, Fang; Wu, Xiao‐Feng

doi:10.1016/j.jcat.2021.03.029

Cited by 9 publications

(12 citation statements)

References 35 publications

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“…On this basis, bismuth-mediated arylation of phenols and bismuth-catalyzed fluorination and oxidative coupling of arylboronic acids and triflate salts have been developed. In addition, a similar process of CO insertion into the bismuth center has also been reported by our group . The key to this strategy lies in suitable oxidants and nucleophiles that can be easily exchanged and eliminated.…”

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confidence: 73%

Sulfonylation of Bismuth Reagents with Sulfinates or SO₂ through Bi^III/Bi^V Intermediates

Zhao

2021

Organometallics

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Studies to explore the catalytic activities of main-group elements are attractive. We report here our study of sulfonylation of bismuth reagents with sulfinates or SO2 surrogates. Under oxidative conditions, triarylbismuthines and sulfinates were transformed into diaryl sulfones. A transition-metal-like two-electron redox process at the Bi center was achieved in this reaction. Sulfur dioxide generated in situ can also replace sulfinates to deliver the corresponding symmetric diaryl sulfones. A rational mechanism for this reaction was also proposed that involves a Bi(III)–Bi(V) manifold.

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confidence: 73%

Sulfonylation of Bismuth Reagents with Sulfinates or SO₂ through Bi^III/Bi^V Intermediates

Zhao

2021

Organometallics

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“…These predicted modes will promote and enhance further synthetic applications in the area of bismacycle Bi(V)/Bi (III). [59][60][61][62]…”

Section: Discussionmentioning

confidence: 99%

Unveiling the origin of the chemoselectivity of bismacycle-mediated C–H arylation of phenols: from mechanism concept to new coupling design

Hussein

2022

Org. Chem. Front.

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“…Looking ahead, we anticipate numerous opportunities for discovery in bismuth redox catalysis: While other elementary steps (e.g., OA, LM, RE) comprising TM catalysis are analogously realized in Bi catalysis, combinations with migratory insertion-type elementary steps are relatively less explored. 28i , 49b , 77 , 74 Incorporating this type of insertion step into a catalytic cycle would enable new transformations, using small molecules as building blocks. Compared to organo–Bi(I), −Bi(III), and −Bi(V) compounds, open-shell −Bi(0), −Bi(II), and −Bi(IV) species are much less explored or unknown.…”

Section: Conclusion and Future Outlookmentioning

confidence: 99%

“…Stoichiometric examples where the aryl ligands on organobismuth(V) complexes are engaged in reactivity can be found in the arylation of organic compounds through oxidative ligand coupling or formal reductive elimination. , In order to advance these stoichiometric reactions to catalysis, the oxidation step (Bi(III) → Bi(V)) should be compatible with other elementary steps, and after ligand coupling, the commonly reactive aryl group must be reincorporated. In 2020, a demonstration of bismuth redox catalysis via canonical organometallic elementary steps in a Bi(III)/Bi(V) platform was described in the catalytic fluorination of aryl boronic esters (Figure A) .…”

Section: High-valent Bi(iii)/bi(v) Catalysismentioning

confidence: 99%

“…In the presence of strong oxidants, these compounds undergo oxidation leading to organobismuth(V) compounds, which have been applied as oxidants in synthesis . Moreover, the labile nature of the Bi(V)–C bond has also been employed in several stoichiometric oxidative ligand coupling events toward C–C or C–X bond formation. , In heterogeneous electrocatalysis or photocatalysis, Bi is frequently encountered as a dopant in materials in order to advance performance (e.g., selectivity and efficiency) in CO 2 reduction, water splitting, and dinitrogen reduction . Despite these seminal reports indicating the rich redox chemistry of bismuth, the development of catalytic redox processes for organic synthesis have been largely overlooked.…”

Section: Introductionmentioning

confidence: 99%

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Bismuth Redox Catalysis: An Emerging Main-Group Platform for Organic Synthesis

2022

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Bismuth has recently been shown to be able to maneuver between different oxidation states, enabling access to unique redox cycles that can be harnessed in the context of organic synthesis. Indeed, various catalytic Bi redox platforms have been discovered and revealed emerging opportunities in the field of main group redox catalysis. The goal of this perspective is to provide an overview of the synthetic methodologies that have been developed to date, which capitalize on the Bi redox cycling. Recent catalytic methods via low-valent Bi(II)/Bi(III), Bi(I)/Bi(III), and high-valent Bi(III)/Bi(V) redox couples are covered as well as their underlying mechanisms and key intermediates. In addition, we illustrate different design strategies stabilizing low-valent and high-valent bismuth species, and highlight the characteristic reactivity of bismuth complexes, compared to the lighter p -block and d -block elements. Although it is not redox catalysis in nature, we also discuss a recent example of non-Lewis acid, redox-neutral Bi(III) catalysis proceeding through catalytic organometallic steps. We close by discussing opportunities and future directions in this emerging field of catalysis. We hope that this Perspective will provide synthetic chemists with guiding principles for the future development of catalytic transformations employing bismuth.

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The first bismuth self-mediated oxidative carbonylative coupling reaction via BiIII/BiV redox intermediates

Cited by 9 publications

References 35 publications

Sulfonylation of Bismuth Reagents with Sulfinates or SO₂ through Bi^III/Bi^V Intermediates

Sulfonylation of Bismuth Reagents with Sulfinates or SO₂ through Bi^III/Bi^V Intermediates

Unveiling the origin of the chemoselectivity of bismacycle-mediated C–H arylation of phenols: from mechanism concept to new coupling design

Bismuth Redox Catalysis: An Emerging Main-Group Platform for Organic Synthesis

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The first bismuth self-mediated oxidative carbonylative coupling reaction via BiIII/BiV redox intermediates

Cited by 9 publications

References 35 publications

Sulfonylation of Bismuth Reagents with Sulfinates or SO2 through BiIII/BiV Intermediates

Sulfonylation of Bismuth Reagents with Sulfinates or SO2 through BiIII/BiV Intermediates

Unveiling the origin of the chemoselectivity of bismacycle-mediated C–H arylation of phenols: from mechanism concept to new coupling design

Bismuth Redox Catalysis: An Emerging Main-Group Platform for Organic Synthesis

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Sulfonylation of Bismuth Reagents with Sulfinates or SO₂ through Bi^III/Bi^V Intermediates

Sulfonylation of Bismuth Reagents with Sulfinates or SO₂ through Bi^III/Bi^V Intermediates