Thermal Nickel-Catalyzed <i>N</i>-Arylation of NH-Sulfoximines with (Hetero)aryl Chlorides Enabled by PhPAd-DalPhos Ligation

Fisher, Samuel A.; Simon, Connor M.; Fox, Peter L.; Cotnam, Michael J.; DeRoy, Patrick L.; Stradiotto, Mark

doi:10.1021/acs.orglett.3c04152

Cited by 3 publications

(1 citation statement)

References 43 publications

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“…Publications from our group appearing in 2023 and 2024 demonstrated (PhPAd-DalPhos)Ni( o -tolyl)Cl to be an effective catalyst system for related nickel-catalyzed cross-coupling of sulfinamides 49 as well as sulfoximines 54 with (hetero)aryl chlorides ( Fig. 10 ).…”

Section: What Can These Dalphos Ligands Do?mentioning

confidence: 99%

The development of cage phosphine ‘DalPhos’ ligands to enable nickel-catalyzed cross-couplings of (hetero)aryl electrophiles

Morrison,

Stradiotto

2024

Chem. Sci.

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Section: What Can These Dalphos Ligands Do?mentioning

confidence: 99%

The development of cage phosphine ‘DalPhos’ ligands to enable nickel-catalyzed cross-couplings of (hetero)aryl electrophiles

Morrison,

Stradiotto

2024

Chem. Sci.

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Mapping Electrophile Chemoselectivity in DalPhos/Nickel N‐Arylation Catalysis: The Unusual Influence of Remote Sterics

Fox,

Choi,

Johnson

et al. 2024

Chemistry A European J

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We disclose herein our evaluation of competitive (hetero)aryl‐X (X: Br > Cl > OTf) reactivity preferences in bisphosphine/Ni‐catalyzed C‐N cross‐coupling catalysis, using furfurylamine as a prototypical nucleophile, and employing DalPhos and DPPF as representative ancillary ligands with established efficacy. Beyond this general (pseudo)halide ranking, other intriguing structure‐reactivity trends were noted experimentally, including the unexpected observation that bulky alkyl (e.g., R = tBu) substitution in para‐R‐aryl‐X electrophiles strongly discourages (pseudo)halide reactivity relative to smaller substituents (e.g., nBu, Et, Me), despite being both remote from, and having a similar electronic influence on, the reacting C‐X bond; such effects on nickel oxidative addition have not been documented previously and were not observed in our comparator reactions presented herein involving palladium. Density functional theory modeling of such PhPAd‐DalPhos/Ni‐catalyzed C‐N cross‐couplings revealed the origins of competitive turnover of C‐Br over C‐Cl, and possible ways in which bulky para‐alkyl substitution might discourage net electrophile uptake/turnover, leading to inversion of halide selectivity.

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Cross-Coupling Reactions with Nickel, Visible Light, and tert-Butylamine as a Bifunctional Additive

Düker,

Philipp,

Lentner

et al. 2024

ACS Catal.

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Transition metal catalysis is crucial for the synthesis of complex molecules, with ligands and bases playing a pivotal role in optimizing cross-coupling reactions. Despite advancements in ligand design and base selection, achieving effective synergy between these components remains challenging. We present here a general approach to nickel-catalyzed photoredox reactions employing tert-butylamine as a cost-effective bifunctional additive, acting as the base and ligand. This method proves effective for C−O and C−N bond-forming reactions with a diverse array of nucleophiles, including phenols, aliphatic alcohols, anilines, sulfonamides, sulfoximines, and imines. Notably, the protocol demonstrates significant applicability in biomolecule derivatization and facilitates sequential one-pot functionalizations. Spectroscopic investigations revealed the robustness of the dynamic catalytic system, while elucidation of structure−reactivity relationships demonstrated how computed molecular properties of both the nucleophile and electrophile correlated to reaction performance, providing a foundation for effective reaction outcome prediction.

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Thermal Nickel-Catalyzed N-Arylation of NH-Sulfoximines with (Hetero)aryl Chlorides Enabled by PhPAd-DalPhos Ligation

Cited by 3 publications

References 43 publications

The development of cage phosphine ‘DalPhos’ ligands to enable nickel-catalyzed cross-couplings of (hetero)aryl electrophiles

The development of cage phosphine ‘DalPhos’ ligands to enable nickel-catalyzed cross-couplings of (hetero)aryl electrophiles

Mapping Electrophile Chemoselectivity in DalPhos/Nickel N‐Arylation Catalysis: The Unusual Influence of Remote Sterics

Cross-Coupling Reactions with Nickel, Visible Light, and tert-Butylamine as a Bifunctional Additive

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