Metal‐Free Reduction of Phosphine Oxides, Sulfoxides, and <i>N</i>‐Oxides with Hydrosilanes using a Borinic Acid Precatalyst

Chardon, Aurélien; Maubert, Orianne; Rouden, Jacques; Blanchet, Jérôme

doi:10.1002/cctc.201700986

Cited by 26 publications

(3 citation statements)

References 61 publications

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“…Borinic acids were employed by Blanchet and co-workers with silane reductants for the metal-free reduction of phosphine oxides, sulfoxides, and amine N -oxides (Scheme ). Analysis of the mechanism indicated that the active catalyst was a borohydride derived from the borinic acid and the silane. Finally, simple boric acid has been used to promote the reduction of quinolines using Hantzsch esters through coordination of the quinoline nitrogen to the boron …”

Section: Other Reactivitymentioning

confidence: 99%

Emergent Organoboron Acid Catalysts

Graham

Raines

2022

J. Org. Chem.

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Organoboron acids are stable, organic-soluble Lewis acids with potential application as catalysts for a wide variety of chemical reactions. In this review, we summarize the utility of boronic and borinic acids, as well as boric acid, as catalysts for organic transformations. Typically, the catalytic processes exploit the Lewis acidity of trivalent boron, enabling the reversible formation of a covalent bond with oxygen. Our focus is on recent developments in the catalysis of dehydration, carbonyl condensation, acylation, alkylation, and cycloaddition reactions. We conclude that organoboron acids have a highly favorable prospectus as the source of new catalysts.

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Section: Other Reactivitymentioning

confidence: 99%

Emergent Organoboron Acid Catalysts

Graham

Raines

2022

J. Org. Chem.

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“…For examples, Cu(OTf) 2 , CeCl 3 , B(C 6 F 5 ) 3 , electrophilic fluorophosphonium, bis(pertrifluoromethylcatecholato)silane, and trityl cations were used as Lewis acid catalysts. Brønsted acids, e.g., diarylphosphoric acid, CF 3 SO 3 H, and borinic acid, were also employed in catalytic deoxygenation of phosphine oxides at elevated temperatures. The recently reported electrochemical reduction of phosphine oxides can also be considered for Lewis acid activation with borate or aluminum cations. , …”

Section: Introductionmentioning

confidence: 99%

Deoxygenation of Phosphine Oxides by P^III/P^V═O Redox Catalysis via Successive Isodesmic Reactions

et al. 2023

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Deoxygenation of phosphine oxides is of great significance to synthesis of phosphorus ligands and relevant catalysts, as well as to the sustainability of phosphorus chemistry. However, the thermodynamic inertness of P�O bonds poses a severe challenge to their reduction. Previous approaches in this regard rely primarily on a type of P�O bond activation with either Lewis/Brønsted acids or stoichiometric halogenating reagents under harsh conditions. Here, we wish to report a novel catalytic strategy for facile and efficient deoxygenation of phosphine oxides via successive isodesmic reactions, whose thermodynamic driving force for breaking the strong P�O bond was compensated by a synchronous formation of another P�O bond. The reaction was enabled by P III /P�O redox sequences with the cyclic organophosphorus catalyst and terminal reductant PhSiH 3 . This catalytic reaction avoids the use of the stoichiometric activator as in other cases and features a broad substrate scope, excellent reactivities, and mild reaction conditions. Preliminary thermodynamic and mechanistic investigations disclosed a dual synergistic role of the catalyst.

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“…More recently Oestreich, Stephan and co‐workers developed a reduction catalyzed by B(C 6 F 5 ) 3 or electrophilic fluorophosphonium cations 1 a‐b , [20] which proved compatible with a broad range of functional groups (Figure 1). Brønsted acids such as phosphoric acids 2 , [21] and TfOH, [22] or borinic acids 3 [23] have recently been introduced as mild catalysts for this reduction. In this context, we report herein a new simple and mild procedure to reduce phosphine oxides into phosphines using a silane as a reducer and a trityl cation as an initiator.…”

Section: Introductionmentioning

confidence: 99%

The Trityl‐Cation Mediated Phosphine Oxides Reduction

et al. 2021

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Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]− as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes.

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Metal‐Free Reduction of Phosphine Oxides, Sulfoxides, and N‐Oxides with Hydrosilanes using a Borinic Acid Precatalyst

Cited by 26 publications

References 61 publications

Emergent Organoboron Acid Catalysts

Emergent Organoboron Acid Catalysts

Deoxygenation of Phosphine Oxides by P^III/P^V═O Redox Catalysis via Successive Isodesmic Reactions

The Trityl‐Cation Mediated Phosphine Oxides Reduction

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Metal‐Free Reduction of Phosphine Oxides, Sulfoxides, and N‐Oxides with Hydrosilanes using a Borinic Acid Precatalyst

Cited by 26 publications

References 61 publications

Emergent Organoboron Acid Catalysts

Emergent Organoboron Acid Catalysts

Deoxygenation of Phosphine Oxides by PIII/PV═O Redox Catalysis via Successive Isodesmic Reactions

The Trityl‐Cation Mediated Phosphine Oxides Reduction

Contact Info

Product

Resources

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Deoxygenation of Phosphine Oxides by P^III/P^V═O Redox Catalysis via Successive Isodesmic Reactions