Nickel-Catalyzed Oxidative Coupling Reaction of Phenyl Benzyl Sulfoxides

Liang, Xiaoxia; Wu, Chen; Zheng, Zhuo; Walsh, Patrick J.

doi:10.1021/acs.organomet.8b00476

Cited by 5 publications

(2 citation statements)

References 77 publications

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“…Walsh and co-workers found that NiXantphos gives 25–48% yields with either (PBu 3 ) 2 NiCl 2 , Ni(cod) 2, or (dppp)NiCl 2 in an oxidative homocoupling of phenyl benzyl sulfoxides (eq ). Other Ni sources and ligands lead to no yield.…”

Section: Miscellaneousmentioning

confidence: 99%

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Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis

et al. 2020

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A critically important process in catalysis is the formation of an active catalyst from the combination of a metal precursor and a ligand, as the efficacy of this reaction governs the amount of active catalyst. This Review is a comprehensive overview of reactions catalyzed by nickel and an added bidentate phosphine, focusing on the steps transforming the combination of precatalyst and ligand into an active catalyst and the potential effects of this transformation on nickel catalysis. Reactions covered include common cross-coupling reactions, such as Suzuki, Heck, Kumada, and Negishi couplings, addition reactions, cycloadditions, C−H functionalizations, polymerizations, hydrogenations, and reductive couplings, among others. Overall, the most widely used nickel precatalyst with free bidentate phosphines is Ni(cod) 2 , which accounts for ∼50% of the reports surveyed, distantly followed by Ni(acac) 2 and Ni(OAc) 2 , which account for ∼10% each. By compiling the reports of these reactions, we have calculated statistics of the usage and efficacy of each ligand with Ni(cod) 2 and other nickel sources. The most common bidentate phosphines are simple, relatively inexpensive ligands, such as DPPE, DCPE, DPPP, and DPPB, along with others with more complex backbones, such as DPPF and Xantphos. The use of expensive chiral phosphines is more scattered, but the most common ligands include BINAP, Me-Duphos, Josiphos, and related analogs.

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Section: Miscellaneousmentioning

confidence: 99%

“…Other Ni sources and ligands lead to no yield. The reaction is optimized using (PBu 3 ) 2 NiCl 2 and NiXantphos to an 82% yield …”

Section: Miscellaneousmentioning

confidence: 99%

Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis

et al. 2020

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A Base‐ and Ligand‐Free Copper‐Catalyzed Oxidative Coupling of Terminal Alkyl Alkynes

Ying

Bao

et al. 2019

ChemistrySelect

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Lewis Acid Promoted Aerobic Oxidative Coupling of Thiols with Phosphonates by Simple Nickel(II) Catalyst: Substrate Scope and Mechanistic Studies

Xue

Zhang

et al. 2019

J. Org. Chem.

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Exploring new catalysts for efficient organic synthesis is among the most attractive topics in chemistry. Here, using Ni(OAc)2/LA as catalyst (LA: Lewis acid), a novel catalyst strategy was developed for oxidative coupling of thiols and phosphonates to phosphorothioates with oxygen oxidant. The present study discloses that when Ni(OAc)2 alone was employed as the catalyst, the reaction proceeded very sluggishly with low yield, whereas adding non-redox-active metal ions such as Y3+ to Ni(OAc)2 dramatically promoted its catalytic efficiency. The promotional effect is highly Lewis acidity dependent on the added Lewis acid, and generally, a stronger Lewis acid provided a better promotional effect. The stopped-flow kinetics confirmed that adding Y(OTf)3 can obviously accelerate the activation of thiols by Ni(II) and next accelerate its reaction with phosphonate to generate the phosphorothioate product. ESI-MS characterizations of the catalyst disclosed the formation of the heterobimetallic Ni(II)/Y(III) species in the catalyst solution. Additionally, this Ni(II)/LA catalyst can be applied in the synthesis of a series of phosphorothioate compounds including several commercial bioactive compounds. This catalyst strategy has clearly supported that Lewis acid can significantly improve the catalytic efficiency of these traditional metal ions in organic synthesis, thus opening up new opportunities in their catalyst design.

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Nickel-Catalyzed Oxidative Coupling Reaction of Phenyl Benzyl Sulfoxides

Cited by 5 publications

References 77 publications

Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis

Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis

A Base‐ and Ligand‐Free Copper‐Catalyzed Oxidative Coupling of Terminal Alkyl Alkynes

Lewis Acid Promoted Aerobic Oxidative Coupling of Thiols with Phosphonates by Simple Nickel(II) Catalyst: Substrate Scope and Mechanistic Studies

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