Direct C(sp<sup>2</sup>)C(sp<sup>3</sup>) Cross‐Coupling of Diaryl Zinc Reagents with Benzylic, Primary, Secondary, and Tertiary Alkyl Halides

Dunsford, Jay J.; Clark, Ewan R.; Ingleson, Michael J.

doi:10.1002/ange.201411403

Cited by 18 publications

(1 citation statement)

References 53 publications

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“…We note that iron is essential for activity, precluding the possibility that catalysis proceeds via a zinc-mediated process. 58 Furthermore, a comparison of reactivity under conditions that allow the zinc-mediated process in both the presence and absence of dpbz showed that the diphosphine retards the rate (Supplementary Figure 162). What then is the role of the phosphine?…”

Section: Phosphine-zinc Speciesmentioning

confidence: 99%

The highly surprising behaviour of diphosphine ligands in iron-catalysed Negishi cross-coupling

et al. 2018

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Iron-catalysed cross-coupling is undergoing explosive development, however, mechanistic understanding lags far behind synthetic methodology. Herein we find the activity of irondiphosphine complexes in the Negishi coupling of benzyl halides is strongly dependent on the diphosphine but the ligand does not appear to be coordinated to the iron during turn-over.This was determined using time-resolved in operando X-ray absorption fine structure spectroscopy, employing a custom-made flow-cell and confirmed by 31 P NMR spectroscopy.While the diphosphine ligands tested are all able to coordinate to iron(II), in the presence of excess zinc(II), as in the catalytic reaction, they coordinate predominantly to the zinc. Furthermore, combined synthetic and kinetic investigations implicate the formation of a putative mixed Fe-Zn(dpbz) species prior to the rate-limiting step of catalysis. These unexpected findings may not only impact upon the field of iron-catalysed Negishi cross-

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Section: Phosphine-zinc Speciesmentioning

confidence: 99%

The highly surprising behaviour of diphosphine ligands in iron-catalysed Negishi cross-coupling

et al. 2018

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Copper‐Catalyzed Cross‐Coupling of Benzylic Bromides with Arylboronic Acids: Synthesis of Diarylalkanes and Preliminary Antifungal Evaluation Against Magnaporthe Grisea

et al. 2020

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Reported herein is the practical synthesis of 1,1‐diarylalkanes motifs via copper‐catalyzed cross‐coupling reaction of benzylic bromides with arylboronic acids under mild conditions. The protocols show broad scope and good functional group tolerance, and are also applicable to complex natural products. Mechanistic study indicates a radical mechanism. Moreover, preliminary antibacterial evaluation against Magnaporthe grisea is also described for the first time.

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Nickel‐Catalyzed Reductive Allylation of Tertiary Alkyl Halides with Allylic Carbonates

Chen

Jia

et al. 2017

Angewandte Chemie

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The construction of all C(sp3) quaternary centers has been successfully achieved under Ni‐catalyzed cross‐electrophile coupling of allylic carbonates with unactivated tertiary alkyl halides. For allylic carbonates bearing C1 or C3 substituents, the reaction affords excellent regioselectivity through the addition of alkyl groups to the unsubstituted allylic carbon terminus. The allylic alkylation method also exhibits excellent functional‐group compatibility, and delivers the products with high E selectivity.

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Direct C(sp²)C(sp³) Cross‐Coupling of Diaryl Zinc Reagents with Benzylic, Primary, Secondary, and Tertiary Alkyl Halides

Cited by 18 publications

References 53 publications

The highly surprising behaviour of diphosphine ligands in iron-catalysed Negishi cross-coupling

The highly surprising behaviour of diphosphine ligands in iron-catalysed Negishi cross-coupling

Copper‐Catalyzed Cross‐Coupling of Benzylic Bromides with Arylboronic Acids: Synthesis of Diarylalkanes and Preliminary Antifungal Evaluation Against Magnaporthe Grisea

Nickel‐Catalyzed Reductive Allylation of Tertiary Alkyl Halides with Allylic Carbonates

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Direct C(sp2)C(sp3) Cross‐Coupling of Diaryl Zinc Reagents with Benzylic, Primary, Secondary, and Tertiary Alkyl Halides

Cited by 18 publications

References 53 publications

The highly surprising behaviour of diphosphine ligands in iron-catalysed Negishi cross-coupling

The highly surprising behaviour of diphosphine ligands in iron-catalysed Negishi cross-coupling

Copper‐Catalyzed Cross‐Coupling of Benzylic Bromides with Arylboronic Acids: Synthesis of Diarylalkanes and Preliminary Antifungal Evaluation Against Magnaporthe Grisea

Nickel‐Catalyzed Reductive Allylation of Tertiary Alkyl Halides with Allylic Carbonates

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Product

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Direct C(sp²)C(sp³) Cross‐Coupling of Diaryl Zinc Reagents with Benzylic, Primary, Secondary, and Tertiary Alkyl Halides